Ketoheteroarylpiperdine and -piperazine derivatives as fungicides

ABSTRACT

Ketoheteroarylpiperidine and -piperazine derivatives of the formula (I), 
                         
in which the symbols A, L 1 , G, X, Y, T and R 1  have the meanings given in the description and agrochemically active salts thereof and their use for controlling phytopathogenic harmful fungi and also processes for preparing compounds of the formula (I).

The present invention relates to novel ketoheteroarylpiperidine and-piperazine derivatives, to processes for their preparation, to theiruse for controlling unwanted microorganisms, in particularphytopathogenic fungi, in crop protection, in the domestic and hygienefield and in the protection of materials, and also to crop protectioncompositions comprising these ketoheteroarylpiperidine and -piperazinederivatives.

It is already known that certain heteroarylpiperidine and -piperazinederivatives can be used as fungicidal crop protection agents (see WO2007/014290, WO 2008/013925, WO 2008/013622, WO 2008/091594, WO2008/091580, WO 2009/055514, WO 2009/094407, WO 2009/094445, WO2009/132785, WO 2010/037479, WO 2010/065579, WO 2010/149275, WO2010/066353, WO 2011/018401, WO 2011/018415). However, in particular atrelatively low application rates, the fungicidal activity of thesecompounds is not always sufficient.

Since the ecological and economical demands made on modern cropprotection agents are increasing constantly, for example with respect toactivity spectrum, toxicity, selectivity, application rate, formation ofresidues and favourable manufacture, and there can furthermore beproblems, for example, with resistances, there is a constant need todevelop novel crop protection agents, in particular fungicides, which,at least in some areas, have advantages over the known ones.

Surprisingly, it has now been found that the presentketoheteroarylpiperidine and -piperazine derivatives achieve at leastsome aspects of the objects mentioned and are suitable for use as cropprotection agents, in particular as fungicides.

The invention relates to compounds of the formula (I)

in which the symbols have the following meanings:

-   A represents phenyl which may contain up to three substituents,    -   where the substituents independently of one another are selected        from R²,        or-   A′ represents optionally benzo-fused unsubstituted or substituted 5-    or 6-membered heteroaryl, where the substituents at carbon are    independently of one another selected from R³ and the substituents    at nitrogen are independently of one another selected from R⁴,-   L¹ represents NR⁵ or C(R⁶)₂,-   X represents CH or nitrogen,-   Y represents sulphur or oxygen,-   G represents:

-   -   where the bond identified by “v” is attached directly to X and        where the bond identified by “w” is attached directly to T,

-   T represents *—C(═O)CH₂—#, *—C(═O)CH₂C(R⁸)₂—#, *—C(═O)CH═CH—#,    *—C(═O)C═C—#, *—

C(═O)CH₂C(═O)—#, *—C═CC(═O)—#, *—CH═CHC(═O)—#, *—CH₂CH₂C(═O)—#,*—C(═S)CH₂*—C(═S)CH₂C(R⁸)₂—#, *—C(═S)CH═CH-4, *—C(═S)C≡C—#,*—C═CC(═S)—#, *—CH═CHC(═S)—#, *—CH₂CH₂C(═S)—#, *—C(═NR⁹)CH₂—#,*—C(═NR⁹)CH₂C(R⁸)₂—#, *—CH₂CH₂C(═NR⁹)—#, *—C(═NR⁹)CH═CH—#,*—CH═CHC(═NR⁹)—#, *—CH—CHC(NOH)—# or *—CH═CHC(NO—C₁-C₄-alkyl)CH₂—#,

-   -   where the bond identified by * is attached directly to G and        where the bond identified by # is attached directly to R¹,

-   R¹ is selected from the group containing R¹ _(a), R¹ _(b), R¹ _(c),    R¹ _(d), R¹ _(e), R¹ _(f), R¹ _(g), or R¹ _(h), where

-   R¹ _(a) represents C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl,    C₂-C₆-alkynyl, C₂-C₈-alkoxyalkyl or C₅-C₉-cycloalkoxyalkyl, or

-   R¹ _(b) represents unsubstituted or substituted C₃-C₁₀-cycloalkyl    -   where the substituents independently of one another are selected        from -Q or R¹⁹ or

-   R¹ _(c) represents unsubstituted or substituted C₅-C₁₀-cycloalkenyl,    -   where the substituents independently of one another are selected        from R¹¹ or

-   R¹ _(d) represents unsubstituted or substituted phenyl,    -   where the substituents independently of one another are selected        from -L²Q or R¹² or

-   R¹ _(e) represents unsubstituted or substituted naphthalen-1-yl,    naphthalen-2-yl, 1,2,3,4-tetrahydronaphthalen-1-yl,    1,2,3,4-tetrahydronaphthalen-2-yl,    5,6,7,8-tetrahydronaphthalen-1-yl,    5,6,7,8-tetrahydronaphthalen-2-yl, decalin-1-yl, decalin-2-yl,    1H-inden-1-yl, 1H-inden-2-yl, 1H-inden-3-yl, 1H-inden-5-yl,    1H-inden-6-yl, 1H-inden-7-yl, indan-1-yl, indan-2-yl, indan-3-yl,    indan-4-yl or indan-5-yl,    -   where the substituents independently of one another are selected        from R¹³ or

-   R¹ _(f) represents an unsubstituted or substituted 5- or 6-membered    heteroaryl radical, where the substituents at carbon independently    of one another are selected from -L²Q or R¹⁴ and the substituents at    nitrogen independently of one another are selected from -L³Q or R¹⁵    or

-   R¹ _(g) represents benzo-fused unsubstituted or substituted 5- or    6-membered heteroaryl, where the substituents at carbon    independently of one another are selected from R¹⁶ and the    substituents at nitrogen independently of one another are selected    from R¹⁷ or

-   R¹ _(h) represents unsubstituted or substituted C₅-C₁₅-heterocyclyl,    where the substituents at carbon independently of one another are    selected from R¹⁸ and the substituents at nitrogen independently of    one another are selected from R¹⁹,

-   L² represents a direct bond, —O—, —C(R²⁰)₂— or —NR²¹—,

-   L³ represents a direct bond or —C(R²⁰)₂—,

-   Q is selected from the group containing Q′, Q″ and Q′″, where    -   Q′ represents phenyl which may contain up to two substituents,        where the substituents independently of one another are selected        from R²² or    -   Q″ represents a 5- or 6-membered heteroaryl radical which may        contain up to two substituents, where the substituents at carbon        independently of one another are selected from R²³ and the        substituents at nitrogen independently of one another are        selected from R²⁴ or    -   Q′″ represents saturated or partially unsaturated        C₃-C₁₀-cycloalkyl,

-   R², R¹² and R²² independently of one another represent halogen,    cyano, hydroxyl, SH, amino, nitro, phenyl, C(═O)H, C(═O)OH,    CONR²⁵R²⁶, NR²⁵R²⁶, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,    C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl,    C₃-C₈-cycloalkyl, C₃-C₈-halocycloalkyl, C₄-C₁₀-alkylcycloalkyl,    C₄-C₁₀-cycloalkylalkyl, C₆-C₁₄-cycloalkylcycloalkyl,    C₄-C₁₀-halocycloalkylalkyl, C₅-C₁₃-alkylcycloalkylalkyl,    C₃-C₈-cycloalkenyl, C₃-C₈-halocycloalkenyl, C₂-C₆-alkoxyalkyl,    C₄-C₁₀-cycloalkoxyalkyl, C₃-C₈-alkoxyalkoxyalkyl,    C₂-C₆-alkylsulphinylalkyl, C₂-C₆-alkylsulphonylalkyl,    C₂-C₆-alkylaminoalkyl, C₃-C₈-dialkylaminoalkyl,    C₂-C₆-haloalkylaminoalkyl, C₄-C₁₀-cycloalkylaminoalkyl,    C₂-C₆-alkylcarbonyl, C₂-C₆-haloalkylcarbonyl,    C₄-C₈-cycloalkylcarbonyl, C₂-C₆-alkoxycarbonyl,    C₄-C₈-cycloalkoxycarbonyl, C₅-C₁₀-cycloalkylalkoxycarbonyl,    C₂-C₆-alkylaminocarbonyl, C₃-C₈-dialkylaminocarbonyl,    C₄-C₈-cycloalkylaminocarbonyl, C₂-C₆-haloalkoxyalkyl,    C₁-C₆-hydroxyallyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy,    C₃-C₈-cycloalkoxy, C₃-C₈-halocycloalkoxy, C₄-C₁₀-cycloalkylalkoxy,    C₃-C₆-alkenyloxy, C₃-C₆-haloalkenyloxy, C₃-C₆-alkynyloxy,    C₃-C₆-haloalkynyloxy, C₂-C₆-alkoxyalkoxy, C₂-C₆-alkylcarbonyloxy,    C₂-C₆-haloalkylcarbonyloxy, C₄-C₈-cycloalkylcarbonyloxy,    C₃-C₆-alkylcarbonylalkoxy, C₁-C₆-alkylthio, C₁-C₆-haloalkylthio,    C₃-C₆-cycloalkylthio, C₁-C₆-alkylsulphinyl,    C₁-C₆-haloalkylsulphinyl, C₁-C₆-alkylsulphonyl,    C₁-C₆-haloalkylsulphonyl, C₃-C₈-cycloalkylsulphonyl,    C₁-C₆-alkylsulphonylamino or C₁-C₆-haloalkylsulphionylamino,

-   R³, R¹⁴, R¹⁶, R¹⁸ and R²³ independently of one another represent    halogen, cyano, hydroxyl, SH, amino, nitro, NR²⁵R²⁶, C₁-C₆-alkyl,    C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl,    C₂-C₆-haloalkynyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl,    C₄-C₁₀-alkyl-cycloalkyl, C₄-C₁₀-cycloalkylalkyl,    C₆-C₁₄-cycloalkylcycloalkyl, C₅-C₁₀-alkylcycloalkylalkyl,    C₂-C₄-alkoxyalkyl, C₂-C₄-alkylcarbonyl, C₂-C₆-alkoxycarbonyl,    C₂-C₆-alkylaminocarbonyl, C₃-C₈-dialkylaminocarbonyl,    C₁-C₄-hydroxyalkyl, C₁-C₄-alkoxy, C₃-C₆-alkenyloxy,    C₃-C₆-alkynyloxy, C₁-C₄-haloalkoxy, C₂-C₆-alkylcarbonyloxy,    C₂-C₆-alkylcarbonylthio, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio,    C₁-C₄-alkylsulphinyl, C₁-C₄-haloalkylsulphinyl,    C₁-C₄-alkylsulphonyl, C₁-C₄-haloalkylsulphonyl,    tri(C₁-C₄-alkyl)silyl or phenyl,

-   R⁴, R¹⁵, R¹⁷, R¹⁹ and R²⁴ independently of one another represent    C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-haloalkyl,    C₃-C₆-haloalkenyl, C₃-C₆-haloalkynyl, C₃-C₆-cycloalkyl,    C₃-C₆-halocycloalkyl, C₄-C₁₀-alkylcycloalkyl,    C₄-C₁₀-cycloalkylalkyl, phenyl, benzyl, C₁-C₄-alkylsulphonyl,    C(═O)H, C₂-C₄-alkylcarbonyloxy, C₂-C₅-alkoxycarbonyl or    C₂-C₃-alkylcarbonyl,

-   R⁵ represents hydrogen or C₁-C₄-alkyl,

-   R⁶ independently of one another represent hydrogen, C₁-C₄-alkyl,    C₁-C₄-haloalkyl, cyclopropyl, halogen,    -   or the two radicals R⁶ together with the carbon atom to which        they are attached form a cyclopropyl ring,

-   R⁷ represents hydrogen, C₁-C₃-alkyl, C₁-C₃-haloalkyl, C₁-C₄-alkoxy,    C₂-C₅-alkoxycarbonyl or halogen,

-   R⁸ independently of one another represent hydrogen or C₁-C₄-alkyl,

-   R⁹ represents OH, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkylamino,    C₂-C₄-dialkylamino, C₁-C₅-alkoxy, C₁-C₄-haloalkoxy or cyclopropyloxy

-   R¹⁰ and R¹¹ independently of one another represent cyano, halogen,    C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl, C₂-C₆-alkenyl,    C₂-C₆-haloalkenyl, C₂-C₆-alkynyl, C₂-C₆-haloalkynyl,    tri(C₁-C₄-alkyl)silyl, phenyl, hydroxyl, oxo, C₁-C₆-alkoxy,    C₁-C₆-haloalkoxy, C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy,    C₁-C₆-alkylthio or C₁-C₆-haloalkylthio,

-   R¹³ independently of one another represent cyano, nitro, halogen,    C₁-C₆-alkyl, C₁-C₄-haloalkyl, C₃-C₆-cycloalkyl, C₂-C₆-alkenyl,    C₂-C₆-haloalkenyl, C₂-C₆-alkynyl, C₃-C₆-haloalkynyl,    tri(C₁-C₄-alkyl)silyl, benzyl, phenyl, hydroxyl, SH, C₁-C₆-alkoxy,    C₁-C₆-haloalkoxy, C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy,    C₁-C₆-alkylthio or C₁-C₆-haloalkylthio,

-   R²⁰ independently of one another represent hydrogen, halogen,    C₁-C₄-alkyl or C₁-C₄-haloalkyl,

-   R²¹ represents C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₅-cycloalkyl,    C₂-C₆-alkylcarbonyl, C₂-C₆-haloalkylcarbonyl, C₂-C₆-alkoxycarbonyl    or C₂-C₆-haloalkoxycarbonyl,

-   R²⁵ and R²⁶ independently of one another represent hydrogen,    C₁-C₄-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₃-haloalkyl,    C₃-C₆-cycloalkyl, benzyl or phenyl,    and also agrochemically active salts thereof.

The invention furthermore provides the use of the compounds of theformula (I) as fungicide.

The ketoheteroarylpiperidine and -piperazine derivatives of the formula(I) according to the invention and their agrochemically active salts arehighly suitable for controlling phytopathogenic harmful fungi. Thecompounds according to the invention mentioned above in particular havepotent fungicidal activity and can be used both in crop protection, inthe domestic and hygiene field and in the protection of materials.

The compounds of the formula (I) can be present both in pure form and asmixtures of various possible isomeric forms, in particular ofstereoisomers, such as E and Z, threo and erythro, and also opticalisomers, such as R and S isomers or atropisomers, and, if appropriate,also of tautomers. What is claimed are both the E and the Z isomers, andalso the threo and erythro, and also the optical isomers, any mixturesof these isomers, and also the possible tautomeric forms.

-   A preferably represents phenyl which may contain up to two    substituents, where the substituents independently of one another    are selected from R² list and    -   R² preferably represents:    -   halogen, cyano, hydroxyl, amino, nitro, C₁-C₆-alkyl,        C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₃-C₈-cycloalkyl, C₁-C₆-haloalkyl,        C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl, C₃-C₆-halocycloalkyl,        C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,        C₁-C₄-alkylsulphonyl, C₁-C₄-haloalkylthio,        C₁-C₄-haloalkylsulphonyl, C₂-C₄-alkoxyalkyl,        C₂-C₅-alkylcarbonyl, C₂-C₆-alkoxycarbonyl,        C₂-C₆-alkylcarbonyloxy or C(═O)H,-   A′ furthermore preferably represents a heteroaromatic radical    selected from the group below: furan-2-yl, furan-3-yl,    thiophen-2-yl, thiophen-3-yl, isoxazol-3-yl, isoxazol-4-yl,    isoxazol-5-yl, pyrrol-1-yl, pyrrol-2-yl, pyrrol-3-yl, oxazol-2-yl,    oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl,    isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, pyrazol-1-yl,    pyrazol-3-yl, pyrazol-4-yl, imidazol-1-yl, imidazol-2-yl,    imidazol-4-yl, 1,2,3-triazol-1-yl, 1,2,4-triazol-1-yl, pyridin-2-yl,    pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl,    pyrazin-2-yl, pyrazin-3-yl, pyrimidin-2-yl, pyrimidin-4-yl or    pyrimidin-5-yl which may contain up to two substituents, where the    substituents independently of one another are selected from R³ and    R⁴ and    -   R³ preferably represents a substituent at carbon:    -   halogen, cyano, hydroxyl, amino, nitro, C₁-C₆-alkyl,        C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₃-C₈-cycloalkyl, C₁-C₆-haloalkyl,        C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl, C₃-C₆-halocycloalkyl,        C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,        C₁-C₄-alkylsulphonyl, C₁-C₄-haloalkylthio,        C₁-C₄-haloalkylsulphonyl, C₂-C₄-alkoxyalkyl,        C₂-C₆-alkoxycarbonyl, C₂-C₆-alkylcarbonyloxy, C(═O)H or phenyl    -   R⁴ preferably represents a substituent at nitrogen:    -   C₁-C₆-alkyl, C₁-C₄-haloalkyl, C₃-C₆-alkenyl, C₃-C₆-haloalkenyl,        C₃-C₆-alkynyl or C₃-C₆-haloalkynyl.-   A particularly preferably represents phenyl which may contain up to    two substituents, where the substituents independently of one    another are selected from R² and    -   R² particularly preferably represents:    -   fluorine, bromine, iodine, chlorine, cyano, nitro, methyl,        ethyl, propyl, 1-methylethyl, 1,1-dimethylethyl,        chlorofluoromethyl, dichloromethyl, dichlorofluoromethyl,        difluoromethyl, trichloromethyl, trifluoromethyl, cyclopropyl,        ethoxy, 1-methylethoxy, propoxy, methoxy, trifluoromethoxy,        difluoromethoxy, 1-methylethylthio, methylthio, ethylthio,        propylthio, difluoromethylthio or trifluoromethylthio,-   A′ particularly preferably represents a heteroaromatic radical    selected from the group below: furan-2-yl, furan-3-yl,    thiophen-2-yl, thiophen-3-yl, isoxazol-3-yl, isoxazol-4-yl,    isoxazol-5-yl, pyrrol-1-yl, pyrrol-2-yl, oxazol-2-yl, oxazol-4-yl,    oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl,    isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, pyrazol-1-yl,    pyrazol-3-yl, pyrazol-4-yl, imidazol-1-yl, imidazol-2-yl,    imidazol-4-yl, 1,2,3-triazol-1-yl, 1,2,4-triazol-1-yl, pyridin-2-yl,    pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl,    pyrimidin-2-yl, pyrimidin-4-yl or pyrimidin-5-yl which may contain    up to two substituents, where the substituents independently of one    another are selected from R³ and R⁴ and    -   R³ particularly preferably represents a substituent at carbon:    -   fluorine, chlorine, bromine, iodine, cyano, nitro, methyl,        ethyl, propyl, 1-methylethyl, 1,1-dimethylethyl,        chlorofluoromethyl, dichloromethyl, dichlorofluoromethyl,        difluoromethyl, trichloromethyl, trifluoromethyl, cyclopropyl,        ethoxy, 1-methylethoxy, propoxy, methoxy, trifluoromethoxy,        difluoromethoxy, 1-methylethylthio, methylthio, ethylthio,        propylthio, difluoromethylthio, trifluoromethylthio or phenyl,    -   R⁴ particularly preferably represents a substituent at nitrogen:    -   methyl, ethyl, propyl, 1-methylethyl, 2,2-trifluoroethyl,        2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,        2-chloro-2-difluoroethyl or 2-chloro-2-fluoroethyl,-   A′ very particularly preferably represents pyrazol-1-yl which may    contain up to two substituents, where the substituents independently    of one another are selected from R³ and    -   R³ very particularly preferably represents    -   methyl, difluoromethyl or trifluoromethyl,-   A furthermore very particularly preferably represents phenyl which    may contain up to two substituents, where the substituents    independently of one another are selected from R² and    -   R² very particularly preferably represents:    -   methyl, ethyl, iodine, chlorine, bromine, fluorine, methoxy,        ethoxy, difluoromethyl or trifluoromethyl,-   G preferably represents G¹ or G²,-   G particularly preferably represents G¹,-   T preferably represents *—C(═O)CH₂—#, *—C(═O)CH₂C(R⁵)₂—#,    *—C(═O)CH═CH—#, *—C(═O)C≡C—#, *—C≡CC(═O)—#, *—CH═CHC(═O)—#,    *—CH₂CH₂C(═O)—#, *—C(═S)CH₂—#, *—C(═S)CH₂C(R⁸)₂—#, *—CH₂CH₂C(═S)—#,    *—C(═NR⁹)CH₂—#, *—C(═NR⁹)CH═CH— #, *—CH═CHC(═NR⁹)—#, *—CH═CHC(NOH)—#    or *—CH═CHC(NO—C₁-C₄-alkyl)CH₂—#,-   T particularly preferably represents *—C(═O)CH₂—#,    *—C(═O)CH₂C(R)₂—#, *—C(═O)CH═CH—#, *—C≡CC(═O)—#, *—CH═CHC(═O)—#,    *—CH₂CH₂C(═O)—#, *—C(═S)CH₂—#, *—C(═S)CH₂C(R⁸)₂—#, *—CH₂CH₂C(═S)—#,    *—C(═NR⁹)CH₂—#, *—C(═NR⁹)CH═CH—#, *—CH═CHC(—NOH)—# or    *—CH═CHC(N—O—C₁-C₄-alkyl)CH₂—#,-   T very particularly preferably represents *—C(═O)CH₂—#,    *—C(═O)CH₂C(CH₃)₂—#, *—C(═O)CH₂CH₂—#, *—C(═O)CH═CH—#, *—C≡CC(═O)—#,    *—CH═CHC(═O)—# or *—CH₂CH₂C(═O)—#, *—C(═NOCH₃)CH₂—#,    *—C(═N—OH)CH═CH—#, *—C(═N—OCH₃)CH═CH—#, or *—CH═CHC(NOH)—#,-   L¹ preferably represents CH₂ or NR⁵, particularly preferably CH₂,-   X preferably represents CH,-   Y preferably represents oxygen,-   R¹ _(a) preferably represents C₁-C₆-alkyl, C₁-C₆-haloalkyl,    C₂-C₆-alkenyl or C₂-C₆-alkynyl, C₂-C₆-alkoxyalkyl,-   R¹ _(b) preferably represents unsubstituted or substituted    C₃-C₁₀-cycloalkyl, where the substituents independently of one    another are selected from -Q or R¹⁰ and    -   R¹⁰ preferably represents:    -   cyano, halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl,        C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl,        C₂-C₆-haloalkynyl, tri(C₁-C₄-alkyl)silyl, hydroxyl, oxo,        C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₃-C₆-alkenyloxy,        C₃-C₆-alkynyloxy, C₁-C₆-haloalkylthio,-   R¹ _(c) preferably represents unsubstituted or substituted    C₅-C₁₀-cycloalkenyl, where the substituents independently of one    another are selected from R¹¹ and    -   R¹¹ preferably represents:    -   cyano, chlorine, fluorine, C₁-C₆-alkyl, C₁-C₆-haloalkyl,        C₃-C₆-cycloalkyl, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl,        C₂-C₆-alkynyl, C₂-C₆-haloalkynyl, phenyl, oxo, C₁-C₆-alkoxy,        C₁-C₆-haloalkoxy, C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy,        C₁-C₆-alkylthio or C₁-C₆-haloalkylthio,-   R¹ _(d) preferably represents unsubstituted or substituted phenyl,    where the substituents independently of one another are selected    from -L²Q or R¹² and    -   R¹² preferably represents:    -   represents halogen, cyano, hydroxyl, SH, amino, nitro, C(═O)H,        C(═O)OH, CONR²⁵R²⁶, NR²⁵R²⁶, C₁-C₆-alkyl, C₂-C₆-alkenyl,        C₂-C₆-alkynyl, C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl,        C₂-C₆-haloalkynyl, C₃-C₈-cycloalkyl, C₃-C₈-halocycloalkyl,        C₄-C₁₀-alkylcycloalkyl, C₄-C₁₀-cycloalkylalkyl,        C₆-C₁₄-cycloalkylcycloalkyl, C₄-C₁₀-halocycloalkylalkyl,        C₅-C₁₀-alkylcycloalkylalkyl, C₃-C₆-cycloalkenyl,        C₃-C₈-halocycloalkenyl, C₂-C₆-alkoxyalkyl,        C₄-C₁₀-cycloalkoxyalkyl, C₃-C₅-alkoxyalkoxyalkyl,        C₂-C₆-alkylthioalkyl, C₂-C₆-alkylsulphinylalkyl,        C₂-C₆-alkylsulphonylalkyl, C₂-C₆-alkylaminoalkyl,        C₃-C₆-dialkylaminoalkyl, C₂-C₆-haloalkylaminoalkyl,        C₄-C₁₀-cycloalkylaminoalkyl, C₂-C₆-alkylcarbonyl,        C₂-C₆-haloalkylcarbonyl, C₄-C₈-cycloalkylcarbonyl,        C₂-C₆-alkoxycarbonyl, C₄-C₈-cycloalkoxycarbonyl,        C₅-C₁₀-cycloalkylalkoxycarbonyl, C₂-C₆-alkylaminocarbonyl,        C₃-C₈-dialkylaminocarbonyl, C₄-C₅-cycloalkylaminocarbonyl,        C₂-C₆-haloalkoxyalkyl, C₁-C₆-hydroxyalkyl, C₁-C₆-alkoxy,        C₁-C₆-haloalkoxy, C₃-C₈-cycloalkoxy, C₃-C₈-halocycloalkoxy,        C₄-C₁₀-cycloalkylalkoxy, C₃-C₆-alkenyloxy, C₃-C₆-haloalkenyloxy,        C₃-C₆-alkynyloxy, C₃-C₆-haloalkynyloxy, C₂-C₆-alkoxyalkoxy,        C₂-C₆-alkylcarbonyloxy, C₂-C₆-haloalkylcarbonyloxy,        C₄-C₈-cycloalkylcarbonyloxy, C₃-C₆-alkylcarbonylalkoxy,        C₁-C₆-alkylthio, C₁-C₆-haloalkylthio, C₃-C₆-cycloalkylthio,        C₁-C₆-alkylsulphinyl, C₁-C₆-haloalkylsulphinyl,        C₁-C₆-alkylsulphonyl, C₁-C₆-haloalkylsulphonyl,        C₃-C₈-cycloalkylsulphonyl, C₁-C₆-alkylsulphonylamino,        C₁-C₆-haloalkylsulphonylamino,-   R¹ _(e) preferably represents unsubstituted or substituted    naphthalen-1-yl, naphthalen-2-yl, 1,2,3,4-tetrahydronaphthalen-1-yl,    1,2,3,4-tetrahydronaphthalen-2-yl,    5,6,7,8-tetrahydronaphthalen-1-yl,    5,6,7,8-tetrahydronaphthalen-2-yl, decalin-1-yl, decalin-2-yl,    1H-inden-1-yl, 1H-inden-2-yl, 1H-inden-3-yl, 1H-inden-4-yl,    1H-inden-6-yl, 1H-inden-7-yl, indan-1-yl, indan-2-yl, indan-3-yl,    indan-4-yl or indan-5-yl, where the substituents independently of    one another are selected from R¹³ and    -   R¹³ preferably represents:    -   cyano, halogen, C₁-C₆-alkyl, C₁-C₄-haloalkyl, C₂-C₆-alkenyl,        C₂-C₆-alkynyl, benzyl, phenyl, C₁-C₆-alkoxy, Q-C₆-haloalkoxy,        C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy or C₁-C₆-alkylthio,-   R¹ _(f) preferably represents an unsubstituted or substituted 5- or    6-membered heteroaryl radical, where the substituents independently    of one another are selected from -L²Q or R¹⁴ and -L³Q or R¹⁵ and    -   R¹⁴ preferably represents a substituent at carbon:    -   halogen, cyano, hydroxyl, SH, amino, nitro, NR²⁵R²⁶,        C₁-C₈-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-haloalkyl,        C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl, C₃-C₆-cycloalkyl,        C₃-C₆-halocycloalkyl, C₄-C₁₅-alkylcycloalkyl,        C₄-C₁₀-cycloalkylalkyl, C₆-C₁₄-cycloalkylcycloalkyl,        C₅-C₁₀-alkylcycloalkylalkyl, C₂-C₄-alkoxyalkyl,        C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy, C₂-C₄-alkylcarbonyl,        C₂-C₆-alkoxycarbonyl, C₂-C₆-alkylaminocarbonyl,        C₃-C₈-dialkylaminocarbonyl, C₁-C₄-hydroxyalkyl, C₁-C₄-alkoxy,        C₁-C₄-haloalkoxy, C₂-C₆-alkylcarbonyloxy,        C₂-C₆-alkylcarbonylthio, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio,        C₁-C₄-alkylsulphinyl, C₁-C₄-haloalkylsulphinyl,        C₁-C₄-alkylsulphonyl, C₁-C₄-haloalkylsulphonyl,    -   R¹⁵ preferably represents a substituent at nitrogen:    -   C₁-C₆-alkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, C₁-C₆-haloalkyl,        C₃-C₆-haloalkenyl, C₃-C₆-haloalkynyl, C₃-C₆-cycloalkyl,        C₃-C₆-halocycloalkyl, C₄-C₁₀-alkylcycloalkyl,        C₄-C₁₀-cycloalkylalkyl, phenyl,-   R¹ _(g) preferably represents a benzo-fused unsubstituted or    substituted 5- or 6-membered heteroaryl, where the substituents    independently of one another are selected from R¹⁶ and R¹⁷ and    -   R¹⁶ preferably represents a substituent at carbon:    -   halogen, cyano, hydroxyl, SH, amino, nitro, NR²⁶R²⁶,        C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-haloalkyl,        C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl, C₃-C₆-cycloalkyl,        C₃-C₆-halocycloalkyl, C₄-C₁₀-alkylcycloalkyl,        C₄-C₁₀-cycloalkylalkyl, C₆-C₁₄-cycloalkylcycloalkyl,        C₆-C₁₀-alkylcycloalkylalkyl, C₂-C₄-alkoxyalkyl,        C₂-C₄-alkylcarbonyl, C₂-C₆-alkoxycarbonyl,        C₂-C₆-alkylaminocarbonyl, C₃-C₈-dialkylaminocarbonyl,        C₁-C₄-hydroxyalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,        C₂-C₆-alkylcarbonyloxy, C₂-C₆-alkylcarbonylthio,        C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₁-C₄-alkylsulphinyl,        C₁-C₄-haloalkylsulphinyl, C₁-C₄-alkylsulphonyl,        C₁-C₄-haloalkylsulphonyl, tri(C₁-C₄-alkyl)silyl or phenyl,    -   R¹⁷ preferably represents a substituent at nitrogen:    -   C₁-C₆-alkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, C₃-C₆-haloalkenyl,        C₃-C₆-haloalkynyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl,        C₄-C₁₀-alkylcycloalkyl, C₄-C₁₀-cycloalkylalkyl or phenyl,-   R¹ _(h) preferably represents unsubstituted or substituted    C₅-C₁₅-heterocyclyl, where possible substituents independently of    one another are selected from R¹⁸ and R¹⁹ and    -   R¹⁸ preferably represents a substituent at carbon:    -   halogen, cyano, hydroxyl, SH, amino, nitro, NR²⁵R²⁶,        C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₂-C₆-haloalkenyl,        C₂-C₆-haloalkynyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl,        C₄-C₁₀-alkylcycloalkyl, C₄-C₁₀-cycloalkylalkyl,        C₆-C₁₄-cycloalkylcycloalkyl, C₅-C₁₀-alkylcycloalkylalkyl,        C₂-C₄-alkoxyalkyl, C₂-C₄-alkyl carbonyl, C₂-C₆-alkoxycarbonyl,        C₂-C₆-alkylaminocarbonyl, C₃-C₈-dialkylaminocarbonyl,        C₁-C₄-hydroxyalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,        C₂-C₆-alkylcarbonyloxy, C₂-C₆-alkylcarbonylthio,        C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₁-C₄-alkylsulphinyl,        C₁-C₄-haloalkylsulphinyl, C₁-C₄-alkylsulphonyl,        C₁-C₄-haloalkylsulphonyl, -tri(C₁-C₄-alkyl)silyl or phenyl,    -   R¹⁹ preferably represents a substituent at nitrogen:    -   C₁-C₆-alkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, C₁-C₆-haloalkyl,        C₃-C₆-haloalkenyl, C₃-C₆-haloalkynyl, C₃-C₆-cycloalkyl,        C₃-C₆-halocycloalkyl, C₄-C₁₀-alkylcycloalkyl,        C₄-C₁₀-cycloalkylalkyl or phenyl,-   R¹ _(a) particularly preferably represents 1,1-dimethylethyl,    3,3-dimethylbutyl, 2,2-dimethylpropyl, 1,2,2-trimethylpropyl,    pentyl, 1-ethylpropyl, butyl, 2-methylpropyl, 1-methylethyl, ethyl,    propyl, 4-methylpentyl or hexyl,-   R¹ _(b) particularly preferably represents cyclopentyl, cyclohexyl    or cycloheptyl, each of which may contain up to two substituents,    where the substituents independently of one another are selected    from R¹⁰ and    -   R¹⁰ particularly preferably represents:    -   cyano, chlorine, fluorine, bromine, iodine, methyl, ethyl,        propyl, 1-methylethyl, 1,1-dimethylethyl, ethenyl, phenyl,        methoxy, ethoxy, propyloxy, trifluoromethoxy, ethynyl,        2-propynyloxy, methylthio, ethylthio or trifluoromethylthio,-   R¹ _(c) particularly preferably represents cyclopentenyl,    cyclohexenyl or cycloheptenyl, each of which may contain up to two    substituents, where the substituents independently of one another    are selected from R¹¹ and    -   R¹¹ particularly preferably represents:    -   methyl, ethyl, methoxy, ethoxy, trifluoromethoxy, ethynyl,        2-propynyloxy, methylthio, ethylthio or trifluoromethylthio,-   R¹ _(d) particularly preferably represents phenyl which may contain    up to three substituents, where the substituents independently of    one another are selected from -L²Q′ or R¹² and    -   R¹² particularly preferably represents:    -   fluorine, chlorine, bromine, iodine, cyano, nitro, methyl,        ethyl, propyl, 1-methylethyl, butyl, 1,1-dimethylethyl,        1,2-dimethylethyl, ethenyl, ethynyl, trifluoromethyl,        difluoromethyl, trichloromethyl, dichloromethyl, cyclopropyl,        methoxy, ethoxy, propoxy, 1-methylethoxy, 1,1-dimethylethoxy,        methylcarbonyl, ethylcarbonyl, trifluoromethylcarbonyl,        methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl,        1-methylethoxycarbonyl, 1,1-dimethylethoxycarbonyl,        2-propenyloxy, 2-propynyloxy, methylthio, ethylthio,        methylsulphinyl or methylsulphonyl,-   R¹ _(e) particularly preferably represents naphthalen-1-yl,    naphthalen-2-yl, 1,2,3,4-tetrahydronaphthalen-1-yl,    1,2,3,4-tetrahydronaphthalen-2-yl,    5,6,7,8-tetrahydronaphthalen-1-yl,    5,6,7,8-tetrahydronaphthalen-2-yl, decalin-1-yl, decalin-2-yl,    1H-inden-1-yl, 1H-inden-2-yl, 1H-inden-3-yl, 1H-inden-4-yl,    1H-inden-5-yl, 1H-inden-6-yl, 1H-inden-7-yl, indan-1-yl, indan-2-yl,    indan-3-yl, indan-4-yl or indan-5-yl which may contain up to three    substituents, where the substituents independently of one another    are selected from R¹³ and    -   R¹³ particularly preferably represents:    -   methyl, methoxy, cyano, fluorine, chlorine, bromine, iodine,-   R¹ _(f) particularly preferably represents furan-2-yl, furan-3-yl,    thiophen-2-yl, thiophen-3-yl, isoxazol-3-yl, isoxazol-4-yl,    isoxazol-5-yl, pyrrol-1-yl, pyrrol-2-yl, oxazol-2-yl, oxazol-4-yl,    oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl,    isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, pyrazol-1-yl,    pyrazol-3-yl, pyrazol-4-yl, imidazol-1-yl, imidazol-2-yl,    imidazol-4-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl,    1,3,4-oxadiazol-2-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl,    1,3,4-thiadiazol-2-yl, 1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl,    1,2,3-triazol-4-yl, 1,2,4-triazol-1-yl, 1,2,4-triazol-3-yl,    pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl,    pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl or    pyrazin-2-yl, which may each contain up to two substituents, where    the substituents independently of one another are selected from R¹⁴    and R¹⁵ and    -   R¹⁴ particularly preferably represents a substituent at carbon:    -   chlorine, fluorine, bromine, iodine, cyano, nitro, methyl,        ethyl, propyl, 1-methylethyl, butyl, 1,1-dimethylethyl, ethenyl,        ethynyl, trifluoromethyl, difluoromethyl, cyclopropyl,        cyclopentyl, cyclohexyl, methylcarbonyl, ethylcarbonyl,        methoxycarbonyl, ethoxycarbonyl, methoxy, ethoxy, propoxy,        1-methylethoxy, 2-propynyloxy, trifluoromethoxy,        methylcarbonyloxy, methylcarbonylthio, methylthio, ethylthio,        trifluoromethylthio, methylsulphinyl, ethylsulphinyl,        trifluoromethylsulphinyl, methylsulphonyl, ethylsulphonyl or        trifluoromethylsulphonyl,    -   R¹⁵ particularly preferably represents a substituent at        nitrogen: -methyl, ethyl, propyl, cyclopropyl, cyclohexyl,        phenyl or 2-propynyl,-   R¹ _(g) particularly preferably represents indol-1-yl, indol-2-yl,    indol-3-yl, indol-4-yl, indol-5-yl, indol-6-yl, indol-7-yl,    benzimidazol-1-yl, benzimidazol-2-yl, benzimidazol-4-yl,    benzimidazol-5-yl, indazol-1-yl, indazol-3-yl, indazol-4-yl,    indazol-5-yl, indazol-6-yl, indazol-7-yl, indazol-2-yl,    1-benzofuran-2-yl, 1-benzofuran-3-yl, 1-benzofuran-4-yl,    1-benzofuran-5-yl, 1-benzofuran-6-yl, 1-benzofuran-7-yl,    1-benzothiophen-2-yl, 1-benzothiophen-3-yl, 1-benzothiophen-4-yl,    1-benzothiophen-5-yl, 1-benzothiophen-6-yl, 1-benzothiophen-7-yl,    1,3-benzothiazol-2-yl, 1,3-benzothiazol-4-yl, 1,3-benzothiazol-5-yl,    1,3-benzothiazol-6-yl, 1,3-benzothiazol-7-yl, 1,3-benzoxazol-2-yl,    1,3-benzoxazol-4-yl, 1,3-benzoxazol-5-yl, 1,3-benzoxazol-6-yl,    1,3-benzoxazol-7-yl, quinolin-2-yl, quinolin-3-yl, quinolin-4-yl,    quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl,    isoquinolin-1-yl, isoquinolin-3-yl, isoquinolin-4-yl,    isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl or    isoquinolin-8-yl, each of which may contain up to two substituents,    where the substituents independently of one another are selected    from R¹⁶ and R¹⁷ and    -   R¹⁶ particularly preferably represents a substituent at carbon:    -   fluorine, chlorine, bromine, iodine, methyl, methoxy,        2-propynyloxy, 2-propenyloxy,    -   R¹⁷ particularly preferably represents a substituent at        nitrogen:    -   methyl, ethyl, propyl, cyclopropyl, cyclohexyl, phenyl or        2-propynyl,-   R¹ _(a) very particularly preferably represents 1,1-dimethylethyl,-   R¹ _(b) very particularly preferably represents cyclohexyl,    cyclopentyl, 2-methylcyclohexyl, 3-methylcyclohexyl or    4-methylcyclohexyl,-   R¹ _(c) very particularly preferably represents cyclohex-3-en-1-yl    or cyclohex-2-en-1-yl,-   R¹ _(d) very particularly preferably represents phenyl which may    contain up to two substituents, where the substituents independently    of one another are selected from R¹² and    -   R¹² very particularly preferably represents:    -   chlorine, fluorine, bromine, iodine, methyl, methoxy, ethoxy,        trifluoromethyl, difluoromethyl, 2-propenyloxy, 2-propynyloxy or        phenyl,-   R¹ _(e) very particularly preferably represents naphthalen-1-yl,    naphthalen-2-yl, 1,2,3,4-tetrahydronaphthalen-1-yl,    1,2,3,4-tetrahydronaphthalen-2-yl,    5,6,7,8-tetrahydronaphthalen-1-yl,    5,6,7,8-tetrahydronaphthalen-2-yl, decalin-2-yl, 1H-inden-1-yl,    1H-inden-2-yl, 1H-inden-3-yl, 1H-inden-4-yl, 1H-inden-5-yl,    1H-inden-6-yl, 1H-inden-7-yl, indan-1-yl, indan-2-yl, indan-3-yl,    indan-4-yl or indan-5-yl,-   R¹ _(f) very particularly preferably represents furan-2-yl,    furan-3-yl, thiophen-2-yl, thiophen-3-yl, isoxazol-3-yl,    isoxazol-4-yl, isoxazol-5-yl, pyrrol-1-yl, pyrrol-2-yl, pyrrol-3-yl,    oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl,    thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl,    pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, imidazol-1-yl,    imidazol-2-yl, imidazol-4-yl, 1,2,3-triazol-1-yl,    1,2,3-triazol-2-yl, 1,2,3-triazol-4-yl, 1,2,4-triazol-1-yl,    1,2,4-triazol-3-yl, 1,2,4-triazol-4-yl, pyridin-2-yl, pyridin-3-yl,    pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl,    pyrimidin-4-yl or pyrimidin-5-yl,-   L² preferably represents a direct bond or —O—,-   L² particularly preferably represents a direct bond,-   L³ preferably represents a direct bond,-   Q′ preferably represents phenyl which may contain up to two    substituents, where the substituents independently of one another    are selected from R²² and    -   R²² preferably represents:    -   fluorine, chlorine, bromine, iodine, cyano, hydroxyl, SH, nitro,        C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl, C₁-C₄-alkoxy,        C₁-C₄-haloalkoxy, C₁-C₄-alkylthio or C₁-C₄-haloalkylthio,-   Q″ preferably represents furan-2-yl, furan-3-yl, thiophen-2-yl,    thiophen-3-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl,    pyrrol-1-yl, pyrrol-2-yl, pyrrol-3-yl, oxazol-2-yl, oxazol-4-yl,    oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl,    isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, pyrazol-1-yl,    pyrazol-3-yl, pyrazol-4-yl, imidazol-1-yl, imidazol-2-yl,    imidazol-4-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl,    1,3,4-oxadiazol-2-yl, tetrazol-5-yl, 1,2,4-thiadiazol-3-yl,    1,2,4-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 1,2,3-triazol-1-yl,    1,2,3-triazol-2-yl, 1,2,3-triazol-4-yl, 1,2,4-triazol-1-yl,    1,2,4-triazol-3-yl, 1,2,4-triazol-4-yl, tetrazol-5-yl, pyridin-2-yl,    pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl,    pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl,    1,3,5-triazin-2-yl or 1,2,4-triazin-3-yl which may contain up to two    substituents, where the substituents independently of one another    are selected from R²³ and R²⁴ and    -   R²³ preferably represents a substituent at carbon:    -   fluorine, chlorine, bromine, iodine, cyano, hydroxyl, SH, nitro,        C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy,        C₁-C₄-haloalkoxy, C₁-C₄-alkylthio or C₁-C₄-haloalkylthio,    -   R²⁴ preferably represents a substituent at nitrogen:    -   C₁-C₆-alkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, C₃-C₆-cycloalkyl or        phenyl,-   Q′ particularly preferably represents phenyl,-   R⁵ preferably represents hydrogen or methyl, ethyl, propyl,    isopropyl, butyl, isobutyl or tert-butyl,-   R⁵ particularly preferably represents hydrogen,-   R⁷ preferably represents hydrogen,-   R⁸ independently of one another preferably represent hydrogen,    methyl or ethyl,-   R⁸ particularly preferably represents hydrogen, methyl,-   R²⁵ and R²⁶ independently of one another preferably represent    hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl or    tert-butyl.

The formula (I) provides a general definition of theketoheteroarylpiperidine and -piperazine derivatives which can be usedaccording to the invention. Preferred radical definitions for theformulae shown above and below are given below. These definitions applyto the end products of the formula (I) and likewise to all intermediates(see also below under “Illustration of the processes andintermediates”).

The radical definitions and explanations stated above in general orstated in preferred ranges can, however, also be combined as desiredwith one another, that is to say between the respective ranges andpreferred ranges. They apply both to the end products and,correspondingly, to precursors and intermediates. Moreover, individualdefinitions may not apply.

Preference is given to those compounds of the formula (I) in which allradicals in each case have the preferred meanings mentioned above.

Particular preference is given to those compounds of the formula (I) inwhich all radicals in each case have the particularly preferred meaningsmentioned above.

Very particular preference is given to those compounds of the formula(I) in which all radicals in each case have the very particularlypreferred meanings mentioned above.

Preference is furthermore given to compounds of the formula (I) in which

-   A represents 3,5-bis(difluoromethyl)-1H-pyrazol-1-yl.

Preference is furthermore given to compounds of the formula (I) in which

-   A represents 5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl.

Preference is furthermore given to compounds of the formula (I) in which

-   A represents 2,5-dimethylphenyl.

Preference is furthermore given to compounds of the formula (I) in which

-   A represents 2-methyl-5-chlorophenyl.

Preference is furthermore given to compounds of the formula (I) in which

-   G represents G¹.

Preference is furthermore given to compounds of the formula (I) in which

-   T represents *—C(═O)CH₂—#.

Preference is furthermore given to compounds of the formula (I) in which

-   T represents *—C(═O)CH₂C(CH₃)₂—#.

Preference is furthermore given to compounds of the formula (I) in which

-   T represents *—C(═O)CH₂CH₂—#.

Preference is furthermore given to compounds of the formula (I) in which

-   T represents *—C(═O)CH═CH—#.

Preference is furthermore given to compounds of the formula (I) in which

-   T represents *—C≡CC(═O)—#.

Preference is furthermore given to compounds of the formula (I) in which

-   T represents *—CH═CHC(═O)—#.

Preference is furthermore given to compounds of the formula (I) in which

-   T represents *—CH₂CH₂C(═O)—#.

Preference is furthermore given to compounds of the formula (I) in which

-   T represents *—C(═NOCH₃)CH₂—#.

Preference is furthermore given to compounds of the formula (I) in which

-   T represents *—CH═CHC(═NOH)—#.

Preference is furthermore given to compounds of the formula (I) in which

-   X represents CH.

Preference is furthermore given to compounds of the formula (I) in which

-   Y represents oxygen.

Preference is furthermore given to compounds of the formula (I) in which

-   L¹ represents NH.

Preference is furthermore given to compounds of the formula (I) in which

-   L¹ represents —CH₂—.

Preference is furthermore given to compounds of the formula (I) in which

-   R⁸ represents hydrogen.

Preference is furthermore given to compounds of the formula (I) in which

-   R⁸ represents methyl.

Preference is furthermore given to compounds of the formula (I) in which

-   R⁵ represents hydrogen.

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents cyclohexyl (R¹ _(b)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents phenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents 2-methoxyphenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents 4-methoxyphenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents 2-ethoxyphenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents naphthalen-1-yl (R¹ _(e)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents tert-butyl (R¹ _(a)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents thiophen-2-yl (R¹ _(f)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents furan-2-yl (R¹ _(f)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents 2-chlorophenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents 2,4-dichlorophenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents 2-bromophenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents 2,6-difluorophenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents 2-iodophenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents 2-methylphenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents 3-methylphenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents cyclopentyl (R¹ _(b)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents 2-fluoro-4-methoxyphenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents 2-bromo-4-fluorphenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in which

-   represents 2,6-dimethoxyphenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents 2-methylcyclohexyl (R¹ _(b)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents 2-(prop-2-yn-1-yloxy)phenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents 2,6-dichlorophenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents 2,6-dimethylphenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents 2,4,6-trifluorophenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents 2-chloro-5-fluorophenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents 2-chloro-6-fluorophenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents 4-fluorophenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in which

-   R¹ represents 3-fluorophenyl (R¹ _(d)).

Preference is furthermore given to compounds of the formula (I) in whichrepresents 2-fluorophenyl (R¹ _(d)).

The radical definitions mentioned above can be combined with one anotheras desired. Moreover, individual definitions may not apply.

Depending on the nature of the substituents defined above, the compoundsof the formula (I) have acidic or basic properties and can form salts,if appropriate also inner salts, or adducts with inorganic or organicacids or with bases or with metal ions. If the compounds of the formula(I) carry amino, alkylamino or other groups which induce basicproperties, these compounds can be reacted with acids to give salts, orthey are directly obtained as salts in the synthesis. If the compoundsof the formula (I) carry hydroxyl, carboxyl or other groups which induceacidic properties, these compounds can be reacted with bases to givesalts. Suitable bases are, for example, hydroxides, carbonates,bicarbonates of the alkali metals and alkaline earth metals, inparticular those of sodium, potassium, magnesium and calcium,furthermore ammonia, primary, secondary and tertiary amines havingC₁-C₄-alkyl groups, mono-, di- and trialkanolamines of C₁-C₄-alkanols,choline and also chlorocholine.

The salts obtainable in this manner also have fungicidal, herbicidal andinsecticidal properties.

Examples of inorganic acids are hydrohalic acids, such as hydrogenfluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide,sulphuric acid, phosphoric acid and nitric acid, and acidic salts, suchas NaHSO₄ and KHSO₄. Suitable organic acids are, for example, formicacid, carbonic acid and alkanoic acids, such as acetic acid,trifluoroacetic acid, trichloroacetic acid and propionic acid, and alsoglycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid,benzoic acid, cinnamic acid, oxalic acid, saturated or mono- ordiunsaturated C₆-C₂₀-fatty acids, sulphuric acid monoalkyl esters,alkylsulphonic acids (sulphonic acids having straight-chain or branchedalkyl radicals of 1 to 20 carbon atoms), arylsulphonic acids oraryldisulphonic acids (aromatic radicals, such as phenyl and naphthyl,which carry one or two sulphonic acid groups), alkylphosphonic acids(phosphonic acids having straight-chain or branched alkyl radicals of 1to 20 carbon atoms), arylphosphonic acids or aryldiphosphonic acids(aromatic radicals, such as phenyl and naphthyl, which carry one or twophosphonic acid radicals), where the alkyl and aryl radicals may carryfurther substituents, for example p-toluenesulphonic acid, salicylicacid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoicacid, etc.

Suitable metal ions are in particular the ions of the elements of thesecond main group, in particular calcium and magnesium, of the third andfourth main group, in particular aluminium, tin and lead, and also ofthe first to eighth transition group, in particular chromium, manganese,iron, cobalt, nickel, copper, zinc and others. Particular preference isgiven to the metal ions of the elements of the fourth period. Here, themetals can be present in the various valencies that they can assume.

Optionally substituted groups can be mono- or polysubstituted, where inthe case of polysubstitutions the substituents can be identical ordifferent.

In the definitions of the symbols given in the formulae above,collective terms were used which are generally representative of thefollowing substituents:

halogen: fluorine, chlorine, bromine and iodine;

alkyl: saturated, straight-chain or branched hydrocarbon radicals having1 to 8 carbon atoms, for example (but not limited thereto) C₁-C₆-alkyl,such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl,2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl,3-methyl-butyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl,1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methyl-pentyl, 2-methylpentyl,3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl,3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and1-ethyl-2-methylpropyl;

alkenyl: unsaturated, straight-chain or branched hydrocarbon radicalshaving 2 to 8 carbon atoms and a double bond in any position, forexample (but not limited thereto) C₂-C₆-alkenyl, such as ethenyl,1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl,3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl,1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl,3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl,3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl,3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl,3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl,1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl,1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl,1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl,4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl,3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl,2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl,1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl,4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl,1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl,2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl,1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl,2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl,1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;

alkynyl: straight-chain or branched hydrocarbon groups having 2 to 8carbon atoms and a triple bond in any position, for example (but notlimited thereto) C₂-C₆-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl,1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl,2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butyryl,1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl,1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl,3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl,1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl,2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl,4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl,1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl,3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl,2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;

alkoxy: saturated, straight-chain or branched alkoxy radicals having 1to 8 carbon atoms, for example (but not limited thereto) C₁-C₆-alkoxy,such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy,1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, pentoxy,1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy,1-ethylpropoxy, hexoxy, 1,1-dimethylpropoxy, 1,2-dimethyl-propoxy,1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy,1,1-dimethyl-butoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy,2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy,1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy,1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy and1-ethyl-2-methylpropoxy;

alkylthio: saturated, straight-chain or branched alkylthio radicalshaving 1 to 8 carbon atoms, for example (but not limited thereto)C₁-C₈-alkylthio, such as methylthio, ethylthio, propylthio,1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio,1,1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio,3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio,1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio,2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio,1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio,2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio,1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio,1,2,2-trimethyl-propylthio, 1-ethyl-1-methylpropylthio and1-ethyl-2-methylpropylthio;

alkoxycarbonyl: an alkoxy group having 1 to 6 carbon atoms (as mentionedabove) which is attached to the skeleton via a carbonyl group (—CO—);

alkylsulphinyl: saturated, straight-chain or branched alkylsulphinylradicals having 1 to 8 carbon atoms, for example (but not limitedthereto) C₁-C₅-alkylsulphinyl, such as methylsulphinyl, ethylsulphinyl,propylsulphinyl, 1-methylethylsulphinyl, butylsulphinyl,1-methylpropylsulphinyl, 2-methylpropylsulphinyl,1,1-dimethylethylsulphinyl, pentylsulphinyl, 1-methylbutylsulphinyl,2-methylbutylsulphinyl, 3-methylbutylsulphinyl,2,2-dimethylpropylsulphinyl, 1-ethylpropylsulphiryl, hexylsulphinyl,1,1-dimethylpropylsulphinyl, 1,2-dimethylpropylsulphinyl,1-methylpentylsulphinyl, 2-methylpentylsulphinyl,3-methylpentylsulphinyl, 4-methylpentylsulphinyl,1,1-dimethylbutylsulphinyl, 1,2-dimethylbutylsulphinyl,1,3-dimethylbutylsulphinyl, 2,2-dimethylbutylsulphinyl,2,3-dimethylbutylsulphinyl, 3,3-dimethylbutylsulphinyl,1-ethylbutylsulphinyl, 2-ethylbutylsulphiryl,1,1,2-trimethylpropylsulphinyl, 1,2,2-trimethylpropylsulphinyl,1-ethyl-1-methylpropylsulphinyl and 1-ethyl-2-methylpropylsulphinyl;

alkylsulphonyl: saturated, straight-chain or branched alkylsulphonylradicals having 1 to 8 carbon atoms, for example (but not limitedthereto) C₁-C₆-alkylsulphonyl, such as methylsulphonyl, ethylsulphonyl,propylsulphonyl, 1-methylethylsulphonyl, butylsulphonyl,1-methylpropylsulphortyl, 2-methylpropylsulphonyl,1,1-dimethylethylsulphonyl, pentylsulphonyl, 1-methylbutylsulphonyl,2-methylbutylsulphonyl, 3-methylbutylsulphotyl,2,2-dimethylpropylsulphonyl, 1-ethylpropylsulphonyl, hexylsulphonyl,1,1-dimethylpropylsulphonyl, 1,2-dimethylpropylsulphonyl,1-methylpentylsulphonyl, 2-methylpentylsulphonyl,3-methylpentylsulphonyl, 4-methylpentylsulphonyl,1,1-dimethylbutylsulphonyl, 1,2-dimethylbutylsulphonyl,dimethylbutylsulphonyl, 2,2-dimethylbutylsulphonyl,2,3-dimethylbutylsulphonyl, 3,3-dimethylbutylsulphonyl,1-ethylbutylsulphonyl, 2-ethylbutylsulphonyl,1,1,2-trimethylpropylsulphonyl, 1,2,2-trimethylpropylsulphonyl,1-ethyl-1-methylpropylsulphonyl and 1-ethyl-2-methylpropylsulphonyl;

cycloalkyl: monocyclic saturated hydrocarbon groups having 3 to 10carbon ring members, for example (but not limited thereto) cyclopropyl,cyclopentyl and cyclohexyl;

haloalkyl: straight-chain or branched alkyl groups having 1 to 8 carbonatoms (as mentioned above), where in these groups some or all of thehydrogen atoms may be replaced by halogen atoms as mentioned above, forexample (but not limited thereto) C₁-C₃-haloalkyl, such as chloromethyl,bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl,difluoromethyl, trifluoromethyl, chlorofluoromethyl,dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl,1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl,2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and1,1,1-trifluoroprop-2-yl;

haloalkoxy: straight-chain or branched alkoxy groups having 1 to 8carbon atoms (as mentioned above), where in these groups some or all ofthe hydrogen atoms may be replaced by halogen atoms as mentioned above,for example (but not limited thereto) C₁-C₃-haloalkoxy, such aschloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy,fluoromethoxy, difluoromethoxy, trifluorornethoxy, chlorofluoromethoxy,dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy,1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy,2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy,2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy,2,2,2-trichloroethoxy, pentafluoroethoxy and 1,1,1-trifluoroprop-2-oxy;

haloalkylthio: straight-chain or branched alkylthio groups having 1 to 8carbon atoms (as mentioned above), where in these groups some or all ofthe hydrogen atoms may be replaced by halogen atoms as mentioned above,for example (but not limited thereto) C₁-C₃-haloalkylthio, such aschlor-omethylthio, bromomethylthio, dichloromethylthio,trichloromethylthio, fluoromethylthio, difluoromethylthio,trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio,chlorodifluoromethylthio, 1-chloroethylthio, 1-bromoethylthio,1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio,2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio,2-chloro-2,2-di-fluoroethylthio, 2,2-dichloro-2-fluoroethylthio,2,2,2-trichloroethylthio, pentafluoroethylthio and1,1,1-trifluoroprop-2-ylthio;

heteroaryl: a 5 or 6-membered fully unsaturated monocyclic ring systemcomprising one to four heteroatoms from the group consisting of oxygen,nitrogen and sulphur; if the ring contains a plurality of oxygen atoms,these are not directly adjacent;

5-membered heteroaryl: which contains one to four nitrogen atoms or oneto three nitrogen atoms and one sulphur or oxygen atom: 5-memberedheteroaryl groups which, in addition to carbon atoms, may contain one tofour nitrogen atoms or one to three nitrogen atoms and one sulphur oroxygen atom as ring members, for example (but not limited thereto)2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl,3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl,4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl,2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl,5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl,1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl,1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl and1,3,4-triazol-2-yl;

5-membered heteroaryl which contains one to four nitrogen atoms and isattached via nitrogen or benzo-fused 5-membered heteroaryl whichcontains one to three nitrogen atoms and is attached via nitrogen:5-membered heteroaryl groups which, in addition to carbon atoms, maycontain one to four nitrogen atoms or one to three nitrogen atoms asring members and in which two adjacent carbon ring members or onenitrogen and one adjacent carbon ring member may be bridged by abuta-1,3-diene-1,4-diyl group in which one or two carbon atoms may bereplaced by nitrogen atoms, in which one or two carbon atoms may bereplaced by nitrogen atoms, where these rings are attached to theskeleton via one of the nitrogen ring members, for example (but notlimited thereto) 1-pyrrolyl, 1-pyrazolyl, 1,2,4-triazol-1-yl,1-imidazolyl, 1,2,3-triazol-1-yl, 1,3,4-triazol-1-yl;

6-membered heteroaryl which contains one to four nitrogen atoms:6-membered heteroaryl groups which, in addition to carbon atoms, maycontain, respectively, one to three and one to four nitrogen atoms asring members, for example (but not limited thereto) 2-pyridinyl,3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl,4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl,1,2,4-triazin-3-yl and 1,2,4,5-tetrazin-3-yl;

benzo-fused 5-membered heteroaryl which contains one to three nitrogenatoms or one nitrogen atom and one oxygen or sulphur atom: for example(but not limited thereto) indol-1-yl, indol-2-yl, indol-3-yl,indol-4-yl, indol-5-yl, indol-6-yl, indol-7-yl, benzimidazol-1-yl,benzimidazol-2-yl, benzimidazol-4-yl, benzimidazol-5-yl, indazol-1-yl,indazol-3-yl, indazol-4-yl, indazol-5-yl, indazol-6-yl, indazol-7-yl,indazol-2-yl, 1-benzofuran-2-yl, 1-benzofuran-3-yl, 1-benzofuran-4-yl,1-benzofuran-5-yl, 1-benzofuran-6-yl, 1-benzofuran-7-yl,1-benzothiophen-2-yl, 1-benzothiophen-3-yl, 1-benzothiophen-4-yl,1-benzothiophen-5-yl, 1-benzothiophen-6-yl, 1-benzothiophen-7-yl,1,3-benzothiazol-2-yl, 1,3-benzothiazol-4-yl, 1,3-benzothiazol-5-yl,1,3-benzothiazol-6-yl, 1,3-benzothiazol-7-yl, 1,3-benzoxazol-2-yl,1,3-benzoxazol-4-yl, 1,3-benzoxazol-5-yl, 1,3-benzoxazol-6-yl and1,3-benzoxazol-7-yl,

benzo-fused 6-membered heteroaryl which contains one to three nitrogenatoms: for example (but not limited thereto) quinolin-2-yl,quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl,quinolin-7-yl, quinolin-8-yl, isoquinolin-1-yl, isoquinolin-3-yl,isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yland isoquinolin-8-yl;

heterocyclyl: a three- to fifteen-membered saturated or partiallyunsaturated heterocycle which contains one to four heteroatoms from thegroup consisting of oxygen, nitrogen and sulphur: mono-, bi- ortricyclic heterocycles which contain, in addition to carbon ringmembers, one to three nitrogen atoms and/or one oxygen or sulphur atomor one or two oxygen and/or sulphur atoms; if the ring contains aplurality of oxygen atoms, these are not directly adjacent; such as, forexample (but not limited thereto), oxiranyl, aziridinyl,2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl,3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl,4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl,4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl,4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl,5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl,2-imidazolidinyl, 4-imidazolidinyl, 1,2,4-oxadiazolidin-3-yl,1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl,1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl,1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl,1,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl,2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl,2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl,2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl,2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl,2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl,2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl,2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl,2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl,2-3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyrazol-1-yl,2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl,2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl,3,4-dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl,3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl,4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl,4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl,2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl,2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl,3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl,3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-piperidinyl,3-piperidinyl, 4-piperidinyl, 1,3-dioxan-5-yl, 2-tetrahydropyranyl,4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl,4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl,5-hexahydropyrimidinyl, 2-piperazinyl, 1,3,5-hexahydrotriazin-2-yl and1,2,4-hexahydrotriazin-3-yl;

When combinations of a plurality of radicals are mentioned, such as, forexample, Cx-Cy-alkylcarbonyl or Cx-Cy-alkoxyalkyl, the term Cx-Cydenotes in each case the sum of all carbon atoms present in the entirefragment. Here, X and Y each represent an integer, the number Y beinggreater than the number X.

Not included are combinations which are against natural laws and whichthe person skilled in the art would therefore exclude based on his/herexpert knowledge. Ring structures having three or more adjacent oxygenatoms, for example, are excluded.

Illustration of the Processes and Intermediates

The ketoheteroarylpiperidine and -piperazine derivatives of the formula(I) can be prepared by various routes. The feasible processes are shownSchemetically below. Unless indicated otherwise, the radicals given havethe meanings given above.

The processes according to the invention for preparing compounds of theformula (I) are, if appropriate, carried out using one or more reactionauxiliaries.

Suitable reaction auxiliaries are, if required, inorganic or organicbases or acid acceptors. These preferably include alkali metal oralkaline earth metal acetates, amides, carbonates, bicarbonates,hydrides, hydroxides or alkoxides, such as, for example, sodium acetate,potassium acetate or calcium acetate, lithium amide, sodium amide,potassium amide or calcium amide, sodium carbonate, potassium carbonateor calcium carbonate, sodium bicarbonate, potassium bicarbonate orcalcium bicarbonate, lithium hydride, sodium hydride, potassium hydrideor calcium hydride, lithium hydroxide, sodium hydroxide, potassiumhydroxide or calcium hydroxide, sodium methoxide, ethoxide, n- ori-propoxide, n-, s- or t-butoxide or potassium methoxide, ethoxide, n-or i-propoxide, n-, s- or t-butoxide; furthermore also basic organicnitrogen compounds, such as, for example, trimethylamine, triethylamine,tripropylamine, tributylamine, ethyldiisopropylamine,N,N-dimethylcyclohexylamine, dicyclohexylamine, ethyldicyclohexylamine,N,N-dimethylaniline, N,N-dimethylbenzylamine, pyridine, 2-methyl-,3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and3,5-dimethylpyridine, 5-ethyl-2-methylpyridine, 4-dimethylaminopyridine,N-methylpiperidine, 1,4-diazabicyclo[2.2.2]octane (DABCO),1,5-diazabicyclo[4.3.0]-non-5-ene (DBN), or1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

If appropriate, the processes according to the invention are carried outusing one or more diluents. Suitable diluents are virtually all inertorganic solvents. These include, in particular, aliphatic and aromatic,optionally halogenated hydrocarbons, such as pentane, hexane, heptane,cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene,xylene, methylene chloride, ethylene chloride, chloroform, carbontetrachloride, chlorobenzene and o-dichlorobenzene, ethers such asdiethyl ether and dibutyl ether, glycol dimethyl ether and diglycoldimethyl ether, tetrahydrofuran and dioxane, ketones, such as acetone,methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone,esters, such as methyl acetate and ethyl acetate, nitriles such as, forexample, acetonitrile and propionitrile, amides such as, for example,dimethylformamide, dimethylacetamide and N-methylpyn-olidone, and alsodimethyl sulphoxide, tetramethylene sulphone and hexamethylphosphoramideand DMPU.

In the processes according to the invention, the reaction temperaturescan be varied within a relatively wide range. In general, the processesare carried out at temperatures between 0° C. and 250° C., preferably attemperatures between 10° C. and 185° C.

The processes according to the invention are generally carried out atatmospheric pressure. However, it is also possible to work at increasedor reduced pressure.

For carrying out the processes according to the invention, the startingmaterials required are in each case generally employed in approximatelyequimolar amounts. However, it is also possible to use a relativelylarge excess of one of the components employed in each case.

One way of producing compounds of the formulae (VIII), (XVIIIb) and(XVIIIa) from corresponding compounds (Vd) is shown in Scheme 1.

The compounds of the formula Vd can be prepared from commerciallyavailable precursors (see, for example, FIG. 1) by procedures describedin the literature (see, for example, Comprehensive HeterocyclicChemistry, Vol. 4-6, A. R. Katritzky and C. W. Rees editors, PergamonPress, New York, 1984; Comprehensive Heterocyclic Chemistry II, Vol.2-4, A. R. Katritzky, C. R. Rees, and E. F. Scruveb editors, PergamonPress, New York, 1996; and the series, The Chemistry of HeterocyclicCompounds, E. C. Taylor, editor, Wiley, New York; WO 2008/064474; WO2008/006794; WO 2006/133216; U.S. Pat. No. 5,234,033 A; WO 2007/039177;WO 2007/014290; Org. Biomol. Chem., 2008, 1904.)

The aldehyde of the formula (VIII) can be prepared from C₁-C₂-alkylesters of the formula (Vd) by reduction with reducing agents (forexample diisobutylaluminium hydride). The reaction is preferably carriedout in tetrahydrofuran at −78° C., under an inert atmosphere (see, forexample, J. Med. Chem., 2001, 2319).

The carboxylic acid of the formula (XVIIIb) can be prepared byhydrolysis of the corresponding C₁-C₂-alkyl ester of the formula (Vd)(cf., for example, WO 2007/014290).

The compounds of the general formula (XVIIIa) are prepared from thecorresponding acids of the formula (XVIIIb) by chlorination usingprocesses known from the literature. (for example Tetrahedron 2005, 61,10827-10852, and the literature cited therein).

One way of preparing compounds of the formula (XIX) from correspondingcompounds (VIII) using an organometallic reagent (XVII) is shown inScheme 2.

The compounds of the formula (XIX) are prepared from the aldehyde of theformula (VIII) by addition of an organometallic reagent R¹—CH₂M¹E(XVII), M¹=Mg, Li or Zn, E=Cl, Br, or I). The reaction is preferablycarried out in tetrahydrofuran or diethyl ether at −78° C.-35° C.Particularly preferably, the reaction is carried out in tetrahydrofuranat −78° C., under an inert atmosphere (see, for example, WO 2007/039177,WO 2006/066109). In the case of organozinc compounds, preference isgiven to using Lewis acids (for example BF₃.Et₂O).

The organometallic reagent (XVII) is commercially available or can beprepared from commercially available precursors by procedures describedin the literature (see, for example, “Handbook of FunctionalizedOrganometallics Vol. 1 and 2”, Ed. P. Knochel, Weinheim, Wiley-VCH,2005, and references cited therein).

The reaction time varies depending on the scale of the reaction and thereaction temperature, but is generally between a couple of minutes and48 hours. After the reaction has ended, the compound (XIX) is separatedfrom the reaction mixture using one of the customary separationtechniques. If required, the compounds are purified byrecrystallization, distillation or chromatography, or they can, ifappropriate, also be used for the next step without prior purification.

One way of preparing compounds of the formula (IVa) from compounds (XIX)is shown in Scheme 3.

Compounds of the formula (IVa) are prepared by oxidation of the alcohol(XIX). Numerous methods for preparing ketones from secondary alcoholscan be found in the literature (see, for example, “Oxidation of Alcoholsto Aldehydes and Ketones”, Gabriel Tojo, Marcos Fernandez, SpringerBerlin, 2006, pages 1-97, and the literature cited therein). Theoxidation is preferably carried out under Swern conditions or usingDess-Martin periodinane (see, for example, Am. Chem. Soc. 1991, 113,7277).

Suitable are all solvents which for their part are not oxidized by theoxidizing agent, such as, for example, dichloromethane, chloroform oracetonitrile, if appropriate in the presence of a reaction auxiliary,for example an acid (e.g. sulphuric acid or hydrochloric acid) or else abase (e.g. triethylamine or pyridine).

The reaction is preferably carried out at room temperature. The reactiontime varies depending on the scale of the reaction and the reactiontemperature, but is generally between a few minutes and 48 hours.

After the reaction has ended, the compound (IVa) is removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallization, distillationor chromatography, or they can, if appropriate, also be used for thenext step without prior purification.

One way of preparing compounds of the formula (Va) from correspondingcompounds (XVIII) is shown in Scheme 4.

A compound of the general formula (Va) is prepared by a couplingreaction with a compound of the general formula (XVIIIa) (where W² ischlorine) and with one of the compounds below: N,O-dimethylhydroxamine,N,O-dimethylhydroxamine HCl salt, dialkylamine or dialkylamine HCl salt,if appropriate in the presence of an acid scavenger/a base (see, forexample, WO 2008/013622, WO 2008/013925 and WO 2006/018188).

At least one equivalent of an acid scavenger/a base (for example Hilnigbase, triethylamine or commercially available polymeric acidscavengers), based on the starting material of the general formula(XVIIIa), is employed. If the starting material is a salt, at least twoequivalents of the acid scavenger are required.

The reaction is usually carried out at temperatures of 0° C. to 100° C.and preferably at 20° C. to 30° C., but it can also be carried out atthe reflux temperature of the reaction mixture. The reaction time variesdepending on the scale of the reaction and the reaction temperature, butis generally between a few minutes and 48 hours.

Alternatively, a compound of the formula (Va) can also be synthesizedfrom the corresponding compound of the formula (XVTHb) (where W²represents hydroxyl) using N,O-dimethylhydroxamine,N,O-dimethylhydroxamine HCl salt, dialkylamine or dialkylamine HCl saltin the presence of a coupling reagent, analogously to proceduresdescribed in the literature (for example Tetrahedron, 2005, 61, 10827,and references cited therein).

Suitable coupling reagents are, for example, peptide coupling reagents(for example N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide mixed with4-dimethylaminopyridine, N-(3-dimethylaminopropyl)-N′-ethylcarbodiimidemixed with 1-hydroxybenzotriazole, bromotripyrrolidinophosphoniumhexafluorophosphate,O-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluroniumhexafluorophosphate, etc.).

If appropriate, a base, such as, for example, triethylamine or Hünigbase can be employed in the reaction.

The reaction is preferably carried out at temperatures of from 0° C. to100° C. and particularly preferably from 0° C. to 30° C. The reactiontime varies depending on the scale of the reaction and the reactiontemperature, but is generally between a number of minutes and 48 hours.

The process D according to the invention is preferably carried out usingone or more diluents. After the reaction has ended, the compounds (Va)are removed from the reaction mixture using one of the customaryseparation techniques. If required, the compounds are purified byrecrystallization, distillation or chromatography, or they can, ifappropriate, also be used for the next step without prior purification.

One way of preparing compounds of the formula (IVa) from correspondingcompounds (Va) or (XVIIIa) using an organometallic reagent (XVII orXVIIa) is shown in Scheme 5.

The compounds of the formula (IVa) are prepared from the amide (Va),where W³ represents NMeOMe or NMe₂ by addition of an organometallicreagent R¹—CH₂M²E (XVII), M²=Mg or Li). The reaction is preferablycarried out in tetrahydrofuran at −78° C., under an inert atmosphere(see, for example, J. Med. Chem., 2009, 52, 1701).

(Va) and the organometallic reagent (where M²=Mg or Li) are employed inequimolar amounts; however, if appropriate, the organometallic reagentcan also be used in excess. The reaction is preferably carried out atroom temperature. The reaction time varies depending on the scale of thereaction and the reaction temperature, but is generally between a fewminutes and 48 hours.

Alternatively, the compounds of the formula (IVa) are prepared from thechloride (XVIHa) by addition of an organozinc reagent (XVIIa), R¹—CH₂ZnE(E=Cl, Br, or I), if appropriate in the presence of a palladiumcatalyst. Preferably, the reaction is carried out in the presence ofPd(PPh₃)₄ or PdCl₂ in tetrahydrofuran at room temperature, under aninert atmosphere (see, for example, WO 2007/070818; Org. Lett., 2008,10, 1107). The amount of catalyst used is 0.1-90 mol % based on thestarting material; preferably, 1-30 mol % of the catalyst, based on thestarting material, are used.

(XVIIIa) and the organozinc compound are used in equimolar amounts.However, the organozinc compound can also be used in excess. Thereaction time varies depending on the scale of the reaction and thereaction temperature, but is generally between a few minutes and 48hours.

The process E according to the invention is preferably carried out usingone or more diluents. After the reaction has ended, the compound (IVa)is removed from the reaction mixture using one of the customaryseparation techniques. If required, the compounds are purified byrecrystallization, distillation or chromatography, or they can, ifappropriate, also be used for the next step without prior purification.

One way of preparing compounds of the formula (XVI) from correspondingcompounds (VIII) using an organometallic reagent (XV) is shown in Scheme6.

Process F is carried out analogously to process B (see above).

One way of preparing compounds of the formula (IVb) from correspondingcompounds (XVI) is shown in Scheme 7.

Process G is carried out analogously to process C (see above).

One way of preparing compounds of the formula (IVb) from correspondingcompounds (Va) or (XVIIIa) using an organometallic reagent (XV) is shownin Scheme 8.

Process H is carried out analogously to process E (see above).

One way of preparing the intermediate (IVc) from compound (IVd) is shownin Scheme 9.

By hydrogenation using a suitable catalyst, a double bond is convertedinto a single bond. The catalyst for process I is selected from thehydrogenation catalysts known from the literature for hydrogenation(“Reductions in Organic Chemistry”, Milo{hacek over (s)} Hudlický, JohnWiley & Sons, 1984), such as, for example, palladium on activated carbonor Pearlmans catalyst (Pd(OH))₂ on activated carbon).

The process I according to the invention is preferably carried out usingone or more diluents. Preferred solvents are N,N-dimethylformamide,ethyl acetate and ethanol.

The amount of catalyst used is 0.1-90 mol % based on the startingmaterial; preferably, 1-30 mol % of the catalyst, based on the startingmaterial, are used. The reaction can be carried out at superatmosphericpressure (1-1000 bar) or preferably at atmospheric pressure. Thereaction is preferably carried out at temperatures of 0° C.-150° C. andparticularly preferably at room temperature. The reaction time variesdepending on the scale of the reaction and the reaction temperature, butis generally between half an hour and 72 hours.

After the reaction has ended, the compounds (IVc) are separated from thereaction mixture by one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallization, distillationor chromatography, or they can, if appropriate, also be used for thenext step without prior purification.

One way of preparing compounds of the formula (IVc) from correspondingcompounds (IVe) is shown in Scheme 10.

By hydrogenation using a suitable catalyst, a triple bond is convertedinto a single bond.

The same process as already described in Scheme 9 (process I) isemployed.

One way of preparing compounds of the formula (IVd) from correspondingcompounds (XIV) using an aldehyde (XIII) is shown in Scheme 11.

Compounds (XIV) can be synthesized from compounds (VIII) by initiallyapplying process B and then process C to compounds of the formula(XIII).

Compounds (XIV) can be synthesized from compounds (Va) by initiallyapplying process E to compounds of the formula (Va).

The aldehyde (XIII) is commercially available or can be prepared fromcommercially available precursors by procedures described in theliterature.

A compound of the general formula (IVd) can be synthesized by an aldolcondensation of a compound having the corresponding general formula(XIV) with an aldehyde (XIII) in the presence of an acid or base (see,for example, Synthetic Communications, 2009, 39, 2789; Organic Letters,2009, 11, 3562; Pharmazie, 1988, 43, 82).

Suitable bases are, for example, LiOH, NaOH or KOH, for example in thepresence of water together with a cosolvent, preferably THF, tolueneand/or methanol, to facilitate dissolution of the ester. The startingmaterial and the base are employed in equimolar amounts; however, thebase may, if required, also be used in excess or in catalytic amounts.

Suitable acids are, for example, H₂SO₄ or HCl, for example in thepresence of water together with a cosolvent, preferably THF, tolueneand/or methanol, to facilitate dissolution of the ester. The startingmaterial and the acid are employed in equimolar amounts; however, theacid may, if required, also be used in excess or in catalytic amounts.

(XIV) and (XIII) are used in equimolar amounts. However, if appropriate,the aldehyde (XIII) may also be used in excess. The reaction ispreferably carried out at temperatures of from 0° C. to 100° C. andparticularly preferably at room temperature. The reaction time variesdepending on the scale of the reaction and the reaction temperature, butis generally between a few minutes and 48 hours.

The process K according to the invention is preferably carried out usingone or more diluents. After the reaction has ended, the compound (IVd)is removed from the reaction mixture using one of the customaryseparation techniques. If required, the compounds are purified byrecrystallization, distillation or chromatography, or they can, ifappropriate, also be used for the next step without prior purification.

One way of preparing compounds of the formula (IVe) from correspondingcompounds (Va or XVIIIa) using an alkyne of the formula (XIIa) is shownin Scheme 12.

Analogously to the method described above (process E), it is possible tosynthesize, using an organometallic reagent (XVIIa), where W⁴ representsZnE, MgE or Li, the compounds (IVe) from compounds (Va).

The organometallic reagent (XIIA) is commercially available or can beprepared from commercially available precursors by procedures describedin the literature (see, for example, “Handbook of FunctionalizedOrganometallics Vol. 1 and 2”, Ed. P. Knochel, Weinheim, Wiley-VCH,2005, and references cited therein).

Alternatively, a compound of the general formula (IVe) can be preparedfrom the starting material of the formula (XVIIIa) by apalladium-catalysed crosscoupling analogously to the proceduresdescribed in the literature (see, for example, Synthesis, 2003, 2815).Preferably, (XVIIIa) is converted into the ketone (IVe) using an alkyneof the formula (XIIa), where W⁴ is H in the presence of a catalyst suchas, for example, [(n-allyl)PdCl]₂, Pd(OAc)₂, PdCl₂(CH₃CN)₂, Pd(PPh₃)₄ orPdCl₂(PPh₃)₂ and also, if appropriate, in the presence of furthercocatalysts such as, for example, CuI, Cs₂CO₃ and triethylamine, forexample in a solvent mixture of DMF or THF at 0-80° C. and under aninert atmosphere. The amount of catalyst used is 0.1-90 mol % based onthe starting material; preferably, 0.5-30 mol % of the catalyst, basedon the starting material, are used.

The alkyne (XIIa) is commercially available or can be prepared fromcommercially available precursors by procedures described in theliterature.

The process L according to the invention is preferably carried out usingone or more diluents. After the reaction has ended, the compound (IVe)is removed from the reaction mixture using one of the customaryseparation techniques. If required, the compounds are purified byrecrystallization, distillation or chromatography, or they can, ifappropriate, also be used for the next step without prior purification.

One way of preparing compounds of the formula (IVf) from correspondingcompounds (IVg) is shown in Scheme 13.

The same process as already described in Scheme 9 (process I) isemployed.

One way of preparing compounds of the formula (IVf) from correspondingcompounds (IVh) is shown in Scheme 14.

The same process as already described in Scheme 9 (process I) isemployed.

One way of preparing compounds of the formula (IVg) from correspondingcompounds (VIII) using a ketone (XI) is shown in Scheme 15.

Process O is carried out analogously to process K.

One way of preparing the intermediate (VI) from compound (VIII) is shownin Scheme 16.

From the literature, it is known that alkynylations of aldehydes can beachieved by a Corey-Fuchs reaction (Tetrahedron Lett., 1972, 36, 3769)or a Seyferth-Gilbert homologization (see, for example, J. Org. Chem.,1996, 61, 2540). Alternatively, the alkyne (VI) can also be preparedfrom the aldehyde (VIII) using Bestmann-Ohira's reagent analogously toliterature procedures (see, for example, Synthesis, 2004, 59).Preferably, alkynylations are carried out using Bestmann-Ohira's reagentin methanol or ethanol in the presence of potassium carbonate or sodiumcarbonate.

The process P according to the invention is preferably carried out usingone or more diluents. All known bases can be used in the reaction. Atleast one equivalent of the base (for example alkali metal and alkalineearth metal oxides, hydroxides and carbonates) has to be added to theBestmann-Ohira reagent, and the base may be used in excess, ifappropriate.

The aldehyde (VIII) and the alkynylating reagent are employed inequimolar amounts; however, the Bestmann-Ohira reagent can, ifappriopriate, be used in excess. The reaction is preferably carried outat temperatures of from −100° C. to 60° C. and particularly preferablyfrom −78° C. to 40° C. The reaction time varies depending on the scaleof the reaction and the reaction temperature, but is generally between anumber of minutes and 48 hours.

After the reaction has ended, the compounds (VT) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallization, distillationor chromatography, or they can, if appropriate, also be used for thenext step without prior purification.

One way of preparing compounds of the formula (IVh) from correspondingcompounds (VI) using a compound of the formula (VIIa) is shown in Scheme17.

Process Q is carried out analogously to process L.

One way of preparing compounds of the formula (IVi) from correspondingcompounds (Vc) using a ketone (XI) is shown in Scheme 18.

A compound of the general formula (IVi) can be synthesized by thereaction of a compound having the corresponding general formula (Vc)with a ketone (XI) in the presence of a base (see, for example, WO2008/004100; Bioorganic & Medicinal Chemistry Letters, 2008, 18(17),4859).

All known suitable bases may be employed. Preference is given to usinglithium hexamethyldisilazide, sodium hexamethyldisilazide, potassiumhexamethyldisilazide, sodium methoxide, potassium methoxide, sodiumethoxide, potassium ethoxide and lithium diisopropylamide for thereaction. Preferably, at least one equivalent of the base has to beadded to the ketone of the general formula (XI); if appropriate, thebase may be added in excess.

The process R according to the invention is preferably carried out usingone or more diluents.

The compound (Vc) and the ketone (XI) are employed in equimolar amounts.The reaction is preferably carried out at temperatures of from −100° C.to 100° C. and particularly preferably from −78° C. to 40° C. Thereaction time varies depending on the scale of the reaction and thereaction temperature, but is generally between a number of minutes and48 hours.

After the reaction has ended, the compounds (IVi) are separated from thereaction mixture by one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallization, distillationor chromatography, or they can, if appropriate, also be used for thenext step without prior purification.

One way of preparing compounds of the formulae (IVj)-(IVp) fromcorresponding compounds (IVa), (IVb), (IVd)-(IVh) is shown in Scheme 19.

The process S according to the invention is preferably carried out usingone or more diluents. The preferred solvents are chloroform and1,2-dimethoxyethare.

Suitable sulphurizing agents are, for example, Lawesson's reagent (seeTetrahedron 1986, 42, 6555-6564, Tetrahedron Lett. 1993, 46, 7459-7462)and phosphorus pentasulphide. The starting material and the sulphurizingagent are employed in equimolar amounts; however, the sulphurizing agentmay, if required, also be used in excess.

The reaction is preferably carried out at temperatures of 0° C.-150° C.and particularly preferably from 0° C. to 100° C. The reaction timevaries depending on the scale of the reaction and the reactiontemperature, but is generally between a number of minutes and 48 hours.

After the reaction has ended, the compounds (IVj)-(IVp) are removed fromthe reaction mixture using one of the customary separation techniques.If required, the compounds are purified by recrystallization,distillation or chromatography.

A compound of the general formula (IVq)-(IVs) can be synthesized by acondensation reaction of a compound of the corresponding general formula(IVa), (IVb) or (IVf) with a substrate of the general formula (XXV), ifappropriate in the presence of an acid, an acid scavenger/a base or abasic ion exchanger.

The compound (XXV) or the corresponding hydrochloric acid salts arecommercially available or can be prepared by processes described in theliterature (see, for example, Chem. Eur. J. 2005, 11, 6974-6981 andChem. Soc. Rev., 2001, 30, 205-213).

If appropriate, an acid such as, for example, hydrochloric acid or abase such as, for example, triethylamine, Hünig base or a basic ionexchanger such as, for example, Amberlyst A21 may be used in thereaction.

The process T according to the invention is preferably carried out usingone or more diluents. The preferred solvent is ethanol.

The reaction is preferably carried out at temperatures of 0° C.-100° C.and particularly preferably from 0° C.-30° C. The reaction time variesdepending on the scale of the reaction and the reaction temperature, butis generally between a number of minutes and 48 hours.

After the reaction has ended, the compounds (IVq)-(IVs) are removed fromthe reaction mixture using one of the customary separation techniques.If required, the compounds are purified by recrystallization,distillation or chromatography, or they can, if appropriate, also beused for the next step without prior purification.

One way of preparing compounds of the formula (II) from correspondingcompounds (IV) is shown in Scheme 21.

A compound of the formula (II) is converted into a compound of theformula (IV) using suitable methods for removing protective groups,which methods are described in the literature (“Protective Groups inOrganic Synthesis”; Third Edition; 1999, 494, and the literature citedtherein).

tert-Butoxycarbonyl and benzyloxycarbonyl protective groups can beremoved in an acidic medium (for example using hydrochloric acid ortrifluoroacetic acid). Acetyl protective groups can be removed underbasic conditions (using, for example, potassium carbonate or caesiumcarbonate). Benzylic protective groups can be removed hydrogenolyticallyusing hydrogen in the presence of a catalyst (for example palladium onactivated carbon).

Acids which can be used for this reaction of deprotectingt-butoxycarbonyl and benzyloxycarbonyl groups are, for example,trifluoroacetic acid, hydrochloric acid or other acids, as described inthe literature (for example “Protective Groups in Organic Synthesis”;Third Edition; 1999; p. 494).

The process U according to the invention is preferably carried out usingone or more diluents. The reaction is preferably carried out attemperatures of from 0° C. to +150° C. and particularly preferably atroom temperature. The reaction time varies depending on the scale of thereaction and the reaction temperature, but is generally between half anhour and 72 hours.

After the reaction has ended, the compounds (II) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallization, distillationor chromatography, or they can, if appropriate, also be used for thenext step without prior purification. Moreover, it is possible toisolate the compound of the general formula (II) as a salt, for exampleas hydrochloride or trifluoroacetate.

One way of preparing compounds of the formula (Ia) from correspondingcompounds (II) using the compounds (III) is shown in Scheme 22.

Compounds (III) can be prepared by processes described in the literature(see, for example, WO 2008/013622 and WO 2008/013925).

A compound of the general formula (Ia) can be synthesized analogously toprocedures described in the literature (see, for example, WO2007/147336) by a coupling reaction of a compound of the correspondinggeneral formula (II) with a substrate of the general formula (III),where W⁵ represents chlorine, if appropriate in the presence of an acidscavenger/a base.

At least one equivalent of an acid scavenger/a base (for example Hünigbase, triethylamine or commercially available polymeric acidscavengers), based on the starting material of the general formula (II)is employed. If the starting material is a salt, at least twoequivalents of the acid scavenger are required.

The starting materials are employed in equimolar amounts. The reactionis preferably carried out at temperatures of from 0° C. to 100° C. andparticularly preferably at from 20° C. to 30° C. The reaction timevaries depending on the scale of the reaction and the reactiontemperature, but is generally between a few minutes and 48 hours.

Alternatively, a compound of the formula (Ia) can also be synthesizedfrom the corresponding compound of the formula (II) using a substrate ofthe formula (III), where W⁵ represents hydroxyl in the presence of acoupling agent analogously to procedures described in the literature(for example Tetrahedron 2005, 61, 10827-10852, and the references citedtherein).

Suitable coupling agents are, for example, peptide coupling agents (forexample N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide mixed with4-dimethylaminopyridine, N-(3-dimethylaminopropyl)-N′-ethylcarbodiimidemixed with 1-hydroxybenzotriazole, bromotripyrrolidinophosphoniumhexafluorophosphate,O-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluroniumhexafluorophosphate, etc.).

The reaction is preferably carried out at temperatures of from 0° C. to100° C. and particularly preferably from 0° C. to 30° C. The reactiontime varies depending on the scale of the reaction and the reactiontemperature, but is generally between a number of minutes and 48 hours.

The process V according to the invention is preferably carried out usingone or more diluents. After the reaction has ended, the compounds (Ia)are removed from the reaction mixture using one of the customaryseparation techniques. If required, the compounds are purified byrecrystallization, distillation or chromatography.

One way of preparing compounds of the formula (Ib) from correspondingcompounds (II) using the compounds (XXIV) is shown in Scheme 23.

A compound of the general formula (Ib) can be synthesized analogously toprocedures described in the literature (see, for example, WO2009/055514) by a coupling reaction of a compound of the correspondinggeneral formula (II) with a substrate of the general formula (XXIV), ifappropriate in the presence of an acid scavenger/a base such as, forexample, triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene or Hünigbase.

The process W according to the invention is preferably carried out usingone or more diluents.

The starting materials are employed in equimolar amounts. The reactionis preferably carried out at temperatures of from 0° C. to 100° C. andparticularly preferably from 20° C. to 30° C. The reaction time variesdepending on the scale of the reaction and the reaction temperature, butis generally between a number of minutes and 48 hours.

After the reaction has ended, the compounds (Ib) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallization, distillationor chromatography.

The carbamoyl and thiocarbamoyl chlorides of the formula (Ii,W⁷=chlorine) required as starting materials for carrying out the processaccording to the invention can be prepared by methods described in theliterature (see, for example, Tetrahedron, 2008, 7605; Journal ofOrganic Chemistry, 2004, 3787; Journal of Organic Chemistry, 1983, 4750;European Journal of Organic Chemistry, 2006, 1177). Typically, thecompounds of the formula (Ii, W⁷=chlorine) are prepared from amines ofthe formula (II) and phosgene, thiophosgene or equivalents thereof.

The carbamoyl- and thiocarbamoylimidazoles of the formula (Ii,W⁷=imidazol-1-yl) required as starting materials for carrying outprocess X according to the invention can be prepared by methodsdescribed in the literature (see, for example, Tetrahedron Letters,2008, 5279; Tetrahedron, 2005, 7153). Typically, the compounds of theformula (Ii, W⁷-imidazol-1-yl) are prepared from amines of the formula(II) and 1,1′-carbonyldiimidazoles or 1,1′-thiocarbonyldiimidazoles.

Process X describes the preparation of compounds of the structure (Ij)by reaction of compounds of the structure (Ii, W⁷=chlorine orimidazol-1-yl) and amines (XXVI).

If appropriate, process X is carried out in the presence of a suitableacid acceptor. Suitable acid acceptors are all customary inorganic ororganic bases. These preferably include the hydrides, hydroxides,amides, alkoxides, acetates, carbonates or bicarbonates of alkalineearth metals or alkali metals, such as, for example, sodium hydride,sodium amide, lithium diisopropylamide, sodium methoxide, sodiumethoxide, potassium tert-butoxide, sodium hydroxide, potassiumhydroxide, sodium acetate, sodium carbonate, potassium carbonate,potassium bicarbonate, sodium bicarbonate or ammonium carbonate, andalso tertiary amines, such as trimethylamine, triethylamine,tributylamine, N,N-diisopropylethylamine, N,N-dimethylaniline,N,N-dimethylbenzylamine, pyridine, N-methylpiperidine,N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane(DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

Alternatively, some of the compounds (Ij) obtained when carrying outprocess X according to the invention can also be obtained without theuse of an acid acceptor as corresponding acid chlorides [(Ij)-HCl](starting material: W⁷=Cl). If required, the compounds (Ij) are releasedby customary methods.

The process X according to the invention is preferably carried out usingone or more diluents. The starting materials are employed in equimolaramounts. The reaction is preferably carried out at temperatures of from0° C. to 100° C. and particularly preferably at from 20° C. to 30° C.The reaction time varies depending on the scale of the reaction and thereaction temperature, but is generally between a few minutes and 48hours.

After the reaction has ended, the compounds (Ij) are removed from thereaction mixture using one of the customary separation techniques. Ifrequired, the compounds are purified by recrystallization, distillationor chromatography.

One way of preparing compounds of the formula (X) from correspondingcompounds (VI) is shown in Scheme 25.

Process Y is carried out analogously to process L.

One way of preparing compounds of the formula (XX) from correspondingcompounds (X) is shown in Scheme 26.

The same process as already described in Scheme 22 (process V) isemployed.

One way of preparing compounds of the formula (XX) from correspondingcompounds (XXI) is shown in Scheme 27.

The same process as already described in Scheme 16 (process P) isemployed.

One way of preparing compounds of the formula (Ic) from correspondingcompounds (XX) is shown in Scheme 28.

The same process as already described in Scheme 12 (process L) isemployed.

One way of preparing compounds of the formula (Id) from correspondingcompounds (Ic) is shown in Scheme 29: process CC.

The same process as already described in Scheme 9 (process I) isemployed.

One way of preparing compounds of the formula (Ie) from correspondingcompounds (XXII) using a compound of the formula (XIII) is shown inScheme 30.

The same process as already described in Scheme 11 (process K) isemployed.

One way of preparing compounds of the formula (If) from correspondingcompounds (Ie) is shown in Scheme 31.

The same process as already described in Scheme 9 (process I) isemployed.

One way of preparing compounds of the formula (Ig) from correspondingcompounds (XXIII) using a compound of the formula (XIIb) is shown inScheme 32.

The same process as already described in Scheme 12 (process L) isemployed.

One way of preparing compounds of the formula (If) from correspondingcompounds (Ig) is shown in Scheme 33.

The same process as already described in Scheme 9 (process I) isemployed.

One way of preparing compounds of the formula (Ih) from correspondingcompounds (XXI) using a ketone (XI) is shown in Scheme 34.

The same process as already described in Scheme 11 (process K) isemployed.

One way of preparing compounds of the formula (Id) from correspondingcompounds (Ih) is shown in Scheme 35.

The same process as already described in Scheme 9 (process I) isemployed.

The invention furthermore provides the non-medicinal use of theketoheteroarylpiperidine and -piperazine derivatives for controllingunwanted microorganisms.

The present invention furthermore relates to a crop protectioncomposition for controlling unwanted fungi, which composition comprisesat least one of the ketoheteroarylpiperidine and -piperazine derivativesof the formula (I). These are preferably fungicidal compositions whichcomprise agriculturally suitable auxiliaries, solvents, carriers,surfactants or extenders.

Moreover, the invention relates to a method for controlling unwantedmicroorganisms, characterized in that ketoheteroarylpiperidine and-piperazine derivatives of the formula (I) according to the inventionare applied to the phytopathogenic fungi and/or their habitat.

According to the invention, a carrier is a natural or synthetic organicor inorganic substance with which the active compounds are mixed orbonded for better applicability, in particular for application to plantsor plant parts or seed. The carrier, which may be solid or liquid, isgenerally inert and should be suitable for use in agriculture.

Suitable solid or liquid carriers are: for example ammonium salts andground natural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as finely divided silica, alumina and natural orsynthetic silicates, resins, waxes, solid fertilizers, water, alcohols,especially butanol, organic solvents, mineral and vegetable oils andderivatives of these. Mixtures of such carriers may also be used.Suitable solid carriers for granules are: for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepiolite,dolomite, and synthetic granules of inorganic and organic meals, andalso granules of organic material such as sawdust, coconut shells, maizecobs and tobacco stalks.

Suitable liquefied gaseous extenders or carriers are liquids which aregaseous at ambient temperature and under atmospheric pressure, forexample aerosol propellants, such as halogenated hydrocarbons, and alsobutane, propane, nitrogen and carbon dioxide.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other possible additivesare mineral and vegetable oils.

If the extender used is water, it is also possible to employ, forexample, organic solvents as auxiliary solvents. Essentially, suitableliquid solvents are: aromatics such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes or dichloromethane,aliphatic hydrocarbons such as cyclohexane or paraffins, for examplemineral oil fractions, mineral and vegetable oils, alcohols such asbutanol or glycol and their ethers and esters, ketones such as acetone,methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, stronglypolar solvents such as dimethylformamide and dimethyl sulphoxide, andalso water.

The compositions according to the invention may comprise additionalfurther components, such as, for example, surfactants. Suitablesurfactants are emulsifiers and/or foam formers, dispersants or wettingagents having ionic or nonionic properties, or mixtures of thesesurfactants. Examples of these are salts of polyacrylic acid, salts oflignosulphonic acid, salts of phenolsulphonic acid ornaphthalenesulphonic acid, polycondensates of ethylene oxide with fattyalcohols or with fatty acids or with fatty amines, substituted phenols(preferably alkylphenols or arylphenols), salts of sulphosuccinicesters, taurine derivatives (preferably alkyl taurates), phosphoricesters of polyethoxylated alcohols or phenols, fatty esters of polyols,and derivatives of the compounds containing sulphates, sulphonates andphosphates, for example alkylaryl polyglycol ethers, alkylsulphonates,alkyl sulphates, arylsulphonates, protein hydrolysates, lignosulphitewaste liquors and methylcellulose. The presence of a surfactant isrequired if one of the active compounds and/or one of the inert carriersis insoluble in water and when the application takes place in water. Theproportion of surfactants is between 5 and 40 percent by weight of thecomposition according to the invention.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic colorants suchas alizarin colorants, azo colorants and metal phthalocyanine colorants,and tax nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

If appropriate, other additional components may also be present, forexample protective colloids, binders, adhesives, thickeners, thixotropicsubstances, penetrants, stabilizers, sequestering agents, complexformers. In general, the active compounds can be combined with any solidor liquid additive customarily used for formulation purposes.

The formulations generally comprise between 0.05 and 99% by weight, 0.01and 98% by weight, preferably between 0.1 and 95% by weight,particularly preferably between 0.5 and 90% of active compound, veryparticularly preferably between 10 and 70% by weight.

The active compounds or compositions according to the invention can beused as such or, depending on their respective physical and/or chemicalproperties, in the form of their formulations or the use forms preparedtherefrom, such as aerosols, capsule suspensions, cold-foggingconcentrates, warm-fogging concentrates, encapsulated granules, finegranules, flowable concentrates for the treatment of seed, ready-to-usesolutions, dustable powders, emulsifiable concentrates, oil-in-wateremulsions, water-in-oil emulsions, macrogranules, microgranules,oil-dispersible powders, oil-miscible flowable concentrates,oil-miscible liquids, foams, pastes, pesticide-coated seed, suspensionconcentrates, suspoemulsion concentrates, soluble concentrates,suspensions, wettable powders, soluble powders, dusts and granules,water-soluble granules or tablets, water-soluble powders for thetreatment of seed, wettable powders, natural products and syntheticsubstances impregnated with active compound, and alsomicroencapsulations in polymeric substances and in coating materials forseed, and also ULV cold-fogging and warm-fogging formulations.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds with at least one customaryextender, solvent or diluent, emulsifier, dispersant, and/or binder orfixative, wetting agent, water repellent, if appropriate desiccants andUV stabilizers and, if appropriate, dyes and pigments, defoamers,preservatives, secondary thickeners, adhesives, gibberellins and alsofurther processing auxiliaries.

The compositions according to the invention include not onlyformulations which are already ready for use and can be applied with asuitable apparatus to the plant or the seed, but also commercialconcentrates which have to be diluted with water prior to use.

The active compounds according to the invention can be present as suchor in their (commercial) formulations and in the use forms prepared fromthese formulations as a mixture with other (known) active compounds,such as insecticides, attractants, sterilants, bactericides, acaricides,nematicides, fungicides, growth regulators, herbicides, fertilizers,safeners and/or semiochemicals.

The treatment according to the invention of the plants and plant partswith the active compounds or compositions is carried out directly or byaction on their surroundings, habitat or storage space using customarytreatment methods, for example by dipping, spraying, atomizing,irrigating, evaporating, dusting, fogging, broadcasting, foaming,painting, spreading-on, watering (drenching), drip irrigating and, inthe case of propagation material, in particular in the case of seeds,furthermore as a powder for dry seed treatment, a solution for seedtreatment, a water-soluble powder for slurry treatment, by incrusting,by coating with one or more coats, etc. It is furthermore possible toapply the active compounds by the ultra-low volume method or to injectthe active compound preparation or the active compound itself into thesoil.

The invention furthermore includes a method for treating seed.

The invention furthermore relates to seed which has been treated inaccordance with one of the methods described in the previous paragraph.The seeds according to the invention are used in methods for theprotection of seed from undesirable fungi. In these methods, seedtreated with at least one active compound according to the invention isemployed.

The active compounds or compositions according to the invention are alsosuitable for treating seed. A large part of the damage to crop plantscaused by harmful organisms is triggered by the infection of the seedduring storage or after sowing both during and after germination of theplant. This phase is particularly critical since the roots and shoots ofthe growing plant are particularly sensitive, and even small damage mayresult in the death of the plant. Accordingly, there is great interestin protecting the seed and the germinating plant by using appropriatecompositions.

The control of phytopathogenic fungi by treating the seed of plants hasbeen known for a long time and is the subject of continuousimprovements. However, the treatment of seed entails a series ofproblems which cannot always be solved in a satisfactory manner. Thus,it is desirable to develop methods for protecting the seed and thegerminating plant which dispense with, or at least reduce considerably,the additional application of crop protection agents after sowing orafter emergence of the plants. It is furthermore desirable to optimizethe amount of active compound employed in such a way as to provideoptimum protection for the seed and the germinating plant from attack byphytopathogenic fungi, but without damaging the plant itself by theactive compound employed. In particular, methods for the treatment ofseed should also take into consideration the intrinsic fungicidalproperties of transgenic plants in order to achieve optimum protectionof the seed and the germinating plant with a minimum of crop protectionagents being employed.

The present invention therefore also relates to a method for theprotection of seed and germinating plants, from attack byphytopathogenic fungi, by treating the seed with a composition accordingto the invention. The invention also relates to the use of thecompositions according to the invention for treating seed for protectingthe seed and the germinating plant against phytopathogenic fungi.Furthermore, the invention relates to seed treated with a compositionaccording to the invention for protection against phytopathogenic fungi.

The control of phytopathogenic fungi which damage plants post-emergenceis carried out primarily by treating the soil and the above-ground partsof plants with crop protection agents. Owing to the concerns regarding apossible impact of the crop protection agents on the environment and thehealth of humans and animals, there are efforts to reduce the amount ofactive compounds applied.

One of the advantages of the present invention is that the particularsystemic properties of the active compounds and compositions accordingto the invention mean that treatment of the seed with these activecompounds and compositions not only protects the seed itself, but alsothe resulting plants after emergence, from phytopathogenic fungi. Inthis manner, the immediate treatment of the crop at the time of sowingor shortly thereafter can be dispensed with.

It is also considered to be advantageous that the active compounds orcompositions according to the invention can be used in particular alsofor transgenic seed where the plant growing from this seed is capable ofexpressing a protein which acts against pests. By treating such seedwith the active compounds or compositions according to the invention,even by the expression of the, for example, insecticidal protein,certain pests may be controlled. Surprisingly, a further synergisticeffect may be observed here, which additionally increases theeffectiveness of the protection against attack by pests.

The compositions according to the invention are suitable for protectingseed of any plant variety which is employed in agriculture, in thegreenhouse, in forests or in horticulture and viticulture. Inparticular, this takes the form of seed of cereals (such as wheat,barley, rye, triticale, sorghum/millet and oats), maize, cotton, soyabeans, rice, potatoes, sunflower, bean, coffee, beet (for example sugarbeet and fodder beet), peanut, oilseed rape, poppy, olive, coconut,cacao, sugar cane, tobacco, vegetables (such as tomato, cucumbers,onions and lettuce), turf and ornamentals (see also hereinbelow). Thetreatment of the seed of cereals (such as wheat, barley, rye, triticaleand oats), maize and rice is of particular importance.

As also described further below, the treatment of transgenic seed withthe active compounds or compositions according to the invention is ofparticular importance. This refers to the seed of plants containing atleast one heterologous gene which allows the expression of a polypeptideor protein having insecticidal properties. The heterologous gene intransgenic seed can originate, for example, from microorganisms of thespecies Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma,Clavibacter, Glomus or Gliocladium. Preferably, this heterologous geneis from Bacillus sp., the gene product having activity against theEuropean corn borer and/or the Western corn rootworm. Particularlypreferably, the heterologous gene originates from Bacillusthuringiensis.

Within the context of the present invention, the composition accordingto the invention is applied to the seed either alone or in a suitableformulation. Preferably, the seed is treated in a state in which it isstable enough to avoid damage during treatment. In general, the seed maybe treated at any point in time between harvest and sowing. The seedusually used has been separated from the plant and freed from cobs,shells, stalks, coats, hairs or the flesh of the fruits. Thus, it ispossible to use, for example, seed which has been harvested, cleaned anddried to a moisture content of less than 15% by weight. Alternatively,it is also possible to use seed which, after drying, has been treated,for example, with water and then dried again.

When treating the seed, care must generally be taken that the amount ofthe composition according to the invention applied to the seed and/orthe amount of further additives is chosen in such a way that thegermination of the seed is not adversely affected, or that the resultingplant is not damaged. This must be borne in mind in particular in thecase of active compounds which can have phytotoxic effects at certainapplication rates.

The compositions according to the invention can be applied directly,i.e. without containing any other components and undiluted. In general,it is preferred to apply the compositions to the seed in the form of asuitable formulation. Suitable formulations and methods for treatingseed are known to the person skilled in the art and are described, forexample, in the following documents: U.S. Pat. No. 4,272,417 A, U.S.Pat. No. 4,245,432 A, U.S. Pat. No. 4,808,430 A, U.S. Pat. No. 5,876,739A, US 2003/0176428 A1, WO 2002/080675 A1, WO 2002/028186 A2.

The active compounds which can be used in accordance with the inventioncan be converted into the customary seed-dressing formulations, such assolutions, emulsions, suspensions, powders, foams, slurries or othercoating compositions for seed, and also ULV formulations.

These formulations are prepared in a known manner, by mixing the activecompounds with customary additives such as, for example, customaryextenders and also solvents or diluents, colorants, wetting agents,dispersants, emulsifiers, antifoams, preservatives, secondarythickeners, adhesives, gibberellins and also water.

Colorants which may be present in the seed-dressing formulations whichcan be used in accordance with the invention are all colorants which arecustomary for such purposes. In this context, not only pigments, whichare sparingly soluble in water, but also dyes, which are soluble inwater, may be used. Examples which may be mentioned are the colorantsknown by the names Rhodamin B, C.I. Pigment Red 112 and C.I. Solvent Red1.

Suitable wetting agents which may be present in the seed-dressingformulations which can be used in accordance with the invention are allsubstances which promote wetting and which are conventionally used forthe formulation of agrochemical active compounds. Preference is given tousing alkylnaphthalenesulphonates, such as diisopropyl- ordiisobutylnaphthalenesulphonates.

Suitable dispersants and/or emulsifiers which may be present in theseed-dressing formulations which can be used in accordance with theinvention are all nonionic, anionic and cationic dispersantsconventionally used for the formulation of agrochemical activecompounds. Preference is given to using nonionic or anionic dispersantsor mixtures of nonionic or anionic dispersants. Suitable nonionicdispersants which may be mentioned are, in particular, ethyleneoxide/propylene oxide block polymers, alkylphenol polyglycol ethers andtristryrylphenol polyglycol ether, and their phosphated or sulphatedderivatives. Suitable anionic dispersants are, in particular,lignosulphonates, polyacrylic acid salts and arylsulphonate/formaldehydecondensates.

Antifoams which may be present in the seed-dressing formulations whichcan be used in accordance with the invention are all foam-inhibitingsubstances conventionally used for the formulation of agrochemicalactive compounds. Silicone antifoams and magnesium stearate canpreferably be used.

Preservatives which may be present in the seed-dressing formulationswhich can be used in accordance with the invention are all substanceswhich can be employed for such purposes in agrochemical compositions.Dichlorophene and benzyl alcohol hemiformal may be mentioned by way ofexample.

Secondary thickeners which may be present in the seed-dressingformulations which can be used in accordance with the invention are allsubstances which can be employed for such purposes in agrochemicalcompositions. Cellulose derivatives, acrylic acid derivatives, xanthan,modified clays and finely divided silica are preferred.

Adhesives which may be present in the seed-dressing formulations whichcan be used in accordance with the invention are all customary binderswhich can be employed in seed-dressing products. Polyvinylpyrrolidone,polyvinyl acetate, polyvinyl alcohol and tylose may be mentioned asbeing preferred.

Gibberellins which can be present in the seed-dressing formulationswhich can be used in accordance with the invention are preferably thegibberellins A1, A3 (=gibberellic acid), A4 and A7; gibberellic acid isespecially preferably used. The gibberellins are known (cf. R. Wegler“Chemie der Pflanzenschutz- and Schädlingsbekämpfungsmittel” [Chemistryof crop protection agents and pesticides], vol. 2, Springer Verlag,1970, p. 401-412).

The seed-dressing formulations which can be used in accordance with theinvention can be employed for the treatment of a wide range of seed,including the seed of transgenic plants, either directly or afterpreviously having been diluted with water. In this context, additionalsynergistic effects may also occur in cooperation with the substancesformed by expression.

All mixers which can conventionally be employed for the seed-dressingoperation are suitable for treating seed with the seed-dressingformulations which can be used in accordance with the invention or withthe preparations prepared therefrom by addition of water. Specifically,a procedure is followed during the seed-dressing operation in which theseed is placed into a mixer, the specific desired amount ofseed-dressing formulations, either as such or after previously havingbeen diluted with water, is added, and everything is mixed until theformulation is distributed uniformly on the seed. If appropriate, thisis followed by a drying process.

The active compounds or compositions according to the invention have apotent fungicidal activity and can be employed for controllingundesirable fungi in crop protection and in the protection of materials.

The ketoheteroarylpiperidine and -piperazine derivatives according tothe invention can be employed in crop protection for controllingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

The fungicidal compositions according to the invention can be used forthe curative or protective control of phytopathogenic fungi.Accordingly, the invention also relates to curative and protectivemethods for controlling phytopathogenic fungi using the active compoundsor compositions according to the invention, which are applied to theseed, the plant or plant parts, the fruit or the soil in which theplants grow.

The compositions according to the invention for controllingphytopathogenic fungi in crop protection comprise an effective, butnon-phytotoxic amount of the active compounds according to theinvention. “Effective, but non-phytotoxic amount” means an amount of thecomposition according to the invention which is sufficient to controlthe fungal disease of the plant in a satisfactory manner or to eradicatethe fungal disease completely, and which, at the same time, does notcause any significant symptoms of phytotoxicity. In general, thisapplication rate may vary within a relatively wide range. It depends ona plurality of factors, for example on the fungus to be controlled, theplant, the climatic conditions and the ingredients of the compositionsaccording to the invention.

The fact that the active compounds are well tolerated by plants at theconcentrations required for controlling plant diseases permits thetreatment of above-ground parts of plants, of propagation stock andseeds, and of the soil.

All plants and plant parts can be treated in accordance with theinvention. By plants are understood here all plants and plantpopulations such as desired and undesired wild plants or crop plants(including naturally occurring crop plants). Crop plants can be plantswhich can be obtained by conventional breeding and optimization methodsor by biotechnological and genetic engineering methods or combinationsof these methods, including the transgenic plants and including theplant varieties which can or cannot be protected by varietal propertyrights. Plant parts are to be understood as meaning all parts and organsof plants above and below the ground, such as shoot, leaf, flower androot, examples which may be mentioned being leaves, needles, stalks,stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes.Parts of plants also include harvested crops and vegetative andgenerative propagation material, for example seedlings, tubers,rhizomes, cuttings and seeds.

The active compounds according to the invention are suitable for theprotection of plants and plant organs, for increasing the harvestyields, for improving the quality of the harvested crop, while beingwell tolerated by plants, having favourable toxicity to warm-bloodedspecies and being environmentally friendly. They may be preferablyemployed as crop protection agents. They are active against normallysensitive and resistant species and also against all or some stages ofdevelopment.

The following plants may be mentioned as plants which can be treatedaccording to the invention: cotton, flax, grapevine, fruit, vegetables,such as Rosaceae sp. (for example pome fruits such as apples and pears,but also stone fruits such as apricots, cherries, almonds and peaches,and soft fruits such as strawberries), Ribesioidae sp., Juglandaceaesp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp.,Oleaceae sp., Acyimidaceae sp., Lauraceae sp., Musaceae sp. (for examplebanana plants and banana plantations), Rubiaceae sp. (for examplecoffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (for examplelemons, oranges and grapefruit); Solanaceae sp. (for example tomatoes),Liliaceae sp., Asteraceae sp. (for example lettuce), Umbelliferae sp.,Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp. (for examplecucumber), Alliaceae sp. (for example leeks, onions), Papilionaceae sp.(for example peas); major crop plants such as Gramineae sp. (for examplemaize, turf, cereals such as wheat, rye, rice, barley, oats, millet andtriticale), Poaceae sp. (for example sugar cane), Asteraceae sp. (forexample sunflower), Brassicaceae sp. (for example white cabbage, redcabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi,small radishes, and also oilseed rape, mustard, horseradish and cress),Fabacae sp. (for example beans, peanuts), Papilionaceae sp. (for examplesoya beans), Solanaceae sp. (for example potatoes), Chenopodiaceae sp.(for example sugar beet, fodder beet, Swiss chard, beetroot); usefulplants and ornamental plants in gardens and forests; and in each casegenetically modified types of these plants.

As already mentioned above, it is possible to treat all plants and theirparts according to the invention. In a preferred embodiment, wild plantspecies and plant cultivars, or those obtained by conventionalbiological breeding methods, such as crossing or protoplast fusion, andalso parts thereof, are treated. In a further preferred embodiment,transgenic plants and plant cultivars obtained by genetic engineering,if appropriate in combination with conventional methods (GeneticallyModified Organisms), and parts thereof are treated. The term “parts” or“parts of plants” or “plant parts” has been explained above.Particularly preferably, plants of the plant cultivars which are in eachcase commercially available or in use are treated according to theinvention. Plant cultivars are to be understood as meaning plants havingnew properties (“traits”) and which have been obtained by conventionalbreeding, by mutagenesis or by recombinant DNA techniques. They can becultivars, varieties, bio- or genotypes.

The method of treatment according to the invention can be used in thetreatment of genetically modified organisms (GMOs), e.g. plants orseeds. Genetically modified plants (or transgenic plants) are plants inwhich a heterologous gene has been stably integrated into the genome.The expression “heterologous gene” essentially means a gene which isprovided or assembled outside the plant and when introduced in thenuclear, chloroplastic or mitochondrial genome gives the transformedplant new or improved agronomic or other properties by expressing aprotein or polypeptide of interest or by downregulating or silencingother gene(s) which are present in the plant (using for exampleantisense technology, cosuppression technology or RNAi technology [RNAinterference]). A heterologous gene that is located in the genome isalso called a transgene. A transgene that is defined by its particularlocation in the plant genome is called a transformation or transgenicevent.

Depending on the plant species or plant varieties, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Possible are thus, for example, the followingeffects which exceed the effects which were actually to be expected:reduced application rates and/or a widening of the activity spectrumand/or an increase in the activity of the active compounds andcompositions which can be used according to the invention, better plantgrowth, increased tolerance to high or low temperatures, increasedtolerance to drought or to water or soil salt content, increasedflowering performance, easier harvesting, accelerated maturation, higherharvest yields, bigger fruits, larger plant height, greener leaf colour,earlier flowering, higher quality and/or a higher nutritional value ofthe harvested products, higher sugar concentration within the fruits,better storage stability and/or processability of the harvestedproducts.

At certain application rates, the active compound combinations accordingto the invention may also have a strengthening effect in plants.Accordingly, they are suitable for mobilizing the defence system of theplant against attack by unwanted phytopathogenic fungi and/ormicroorganisms and/or viruses. This may, if appropriate, be one of thereasons for the enhanced activity of the combinations according to theinvention, for example against fungi. Plant-strengthening(resistance-inducing) substances are to be understood as meaning, in thepresent context, also those substances or combinations of substanceswhich are capable of stimulating the defence system of plants in such away that, when subsequently inoculated with unwanted phytopathogenicfungi, the treated plants display a substantial degree of resistance tothese unwanted phytopathogenic fungi. Thus, the substances according tothe invention can be employed for protecting plants against attack bythe abovementioned pathogens within a certain period of time after thetreatment. The period within which protection is brought about generallyextends from 1 to 10 days, preferably 1 to 7 days, after the treatmentof the plants with the active compounds.

Plants and plant varieties which are preferably treated according to theinvention include all plants which have genetic material which impartsparticularly advantageous, useful traits to these plants (whetherobtained by breeding and/or biotechnological means).

Plants and plant varieties which are also preferably treated accordingto the invention are resistant against one or snore biotic stressfactors, i.e. said plants have a better defence against animal andmicrobial pests, such as against nematodes, insects, mites,phytopathogenic fungi, bacteria, viruses and/or viroids.

Plants and plant varieties which may also be treated according to theinvention are those plants which are resistant to one or more abioticstress factors. Abiotic stress conditions may include, for example,drought, cold temperature exposure, heat exposure, osmotic stress,waterlogging, increased soil salinity, increased exposure to minerals,exposure to ozone, exposure to strong light, limited availability ofnitrogen nutrients, limited availability of phosphorus nutrients orshade avoidance.

Plants and plant varieties which may also be treated according to theinvention are those plants characterized by enhanced yieldcharacteristics. Enhanced yield in said plants can be the result of, forexample, improved plant physiology, growth and development, such aswater use efficiency, water retention efficiency, improved nitrogen use,enhanced carbon assimilation, improved photosynthesis, increasedgermination efficiency and accelerated maturation. Yield can furthermorebe affected by improved plant architecture (under stress and non-stressconditions), including early flowering, flowering control for hybridseed production, seedling vigour, plant size, internode number anddistance, root growth, seed size, fruit size, pod size, pod or earnumber, seed number per pod or ear, seed mass, enhanced seed filling,reduced seed dispersal, reduced pod dehiscence and lodging resistance.Further yield traits include seed composition, such as carbohydratecontent, protein content, oil content and composition, nutritionalvalue, reduction in anti-nutritional compounds, improved processabilityand better storage stability.

Plants that may be treated according to the invention are hybrid plantsthat already express the characteristics of heterosis, or hybrid effect,which results in generally higher yield, vigour, health and resistancetowards biotic and abiotic stress factors. Such plants are typicallymade by crossing an inbred male-sterile parent line (the female parent)with another inbred male-fertile parent line (the male parent). Hybridseed is typically harvested from the male-sterile plants and sold togrowers. Male-sterile plants can sometimes (e.g. in corn) be produced bydetasseling (i.e. the mechanical removal of the male reproductive organsor male flowers) but, more typically, male sterility is the result ofgenetic determinants in the plant genome. In that case, and especiallywhen seed is the desired product to be harvested from the hybrid plants,it is typically useful to ensure that male fertility in hybrid plants,which contain the genetic determinants responsible for male sterility,is fully restored. This can be accomplished by ensuring that the maleparents have appropriate fertility restorer genes which are capable ofrestoring the male fertility in hybrid plants that contain the geneticdeterminants responsible for male sterility. Genetic determinants formale sterility may be located in the cytoplasm. Examples of cytoplasmicmale sterility (CMS) were for instance described for Brassica species.However, genetic determinants for male sterility can also be located inthe nuclear genome. Male-sterile plants can also be obtained by plantbiotechnology methods such as genetic engineering. A particularly usefulmeans of obtaining male-sterile plants is described in WO 89/10396 inwhich, for example, a ribonuclease such as a barnase is selectivelyexpressed in the tapetum cells in the stamens. Fertility can then berestored by expression in the tapetum cells of a ribonuclease inhibitorsuch as barstar.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may be treated according to the inventionare herbicide-tolerant plants, i.e. plants made tolerant to one or moregiven herbicides. Such plants can be obtained either by genetictransformation, or by selection of plants containing a mutationimparting such herbicide tolerance.

Herbicide-tolerant plants are for example glyphosate-tolerant plants,i.e. plants made tolerant to the herbicide glyphosate or salts thereof.For example, glyphosate-tolerant plants can be obtained by transformingthe plant with a gene encoding the enzyme5-enolpyruvylshikimate-3-phosphate synthase (EPSPS). Examples of suchEPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonellatyphimurium, the CP4 gene of the bacterium Agrobacterium sp., the genesencoding a petunia EPSPS, a tomato EPSPS, or an Eleusine EPSPS. It canalso be a mutated EPSPS. Glyphosate-tolerant plants can also be obtainedby expressing a gene that encodes a glyphosate oxidoreductase enzyme.Glyphosate-tolerant plants can also be obtained by expressing a genethat encodes a glyphosate acetyltransferase enzyme. Glyphosate-tolerantplants can also be obtained by selecting plants containing naturallyoccurring mutations of the abovementioned genes.

Other herbicide-resistant plants are for example plants which have beenmade tolerant to herbicides inhibiting the enzyme glutamine synthase,such as bialaphos, phosphinothricin or glufosinate. Such plants can beobtained by expressing an enzyme detoxifying the herbicide or a mutantglutamine synthase enzyme that is resistant to inhibition. One suchefficient detoxifying enzyme is, for example, an enzyme encoding aphosphinothricin acetyltransferase (such as the bar or pat protein fromStreptomyces species for example). Plants expressing an exogenousphosphinothricin acetyltransferase have been described.

Further herbicide-tolerant plants are also plants that have been madetolerant to the herbicides inhibiting the enzymehydroxyphenylpyruvatedioxygenase (HPPD).Hydroxyphenylpyruvatedioxygenases are enzymes that catalyse the reactionin which para-hydroxyphenylpyruvate (HPP) is transformed intohomogentisate. Plants tolerant to HPPD inhibitors can be transformedwith a gene encoding a naturally occurring resistant HPPD enzyme, or agene encoding a mutated HPPD enzyme. Tolerance to HPPD inhibitors canalso be obtained by transforming plants with genes encoding certainenzymes enabling the formation of homogentisate despite the inhibitionof the native HPPD enzyme by the HPPD inhibitor. Tolerance of plants toHPPD inhibitors can also be improved by transforming plants with a geneencoding an enzyme prephenate dehydrogenase in addition to a geneencoding an HPPD-tolerant enzyme.

Further herbicide-resistant plants are plants that have been madetolerant to acetolactate synthase (ALS) inhibitors. Known ALS inhibitorsinclude, for example, sulphonylurea, imidazolinone, triazolopyrimidines,pyrimidinyl oxy(thio)benzoates, and/or sulphonylaminocarbonykriazolinoneherbicides. Different mutations in the ALS enzyme (also known asacetohydroxy acid synthase, AHAS) are known to confer tolerance todifferent herbicides and goups of herbicides. The production ofsulphonylurea-tolerant plants and imidazolinone-tolerant plants has beendescribed in the international publication WO 1996/033270. Furthersulphonylurea- and imidazolinone-tolerant plants have also beendescribed, for example in WO 2007/024782.

Other plants tolerant to imidazolinone and/or sulphonylurea can beobtained by induced mutagenesis, by selection in cell cultures in thepresence of the herbicide or by mutation breeding.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are insect-resistant transgenic plants, i.e. plants maderesistant to attack by certain target insects. Such plants can beobtained by genetic transformation, or by selection of plants containinga mutation imparting such insect resistance.

In the present context, the term “insect-resistant transgenic plant”includes any plant containing at least one transgene comprising a codingsequence encoding:

-   1) an insecticidal crystal protein from Bacillus thuringiensis or an    insecticidal portion thereof, such as the insecticidal crystal    proteins listed online at:    -   http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/, or        insecticidal portions thereof, for example proteins of the Cry        protein classes Cry1Ab, Cry1Ac, Cry1F, Cry2Ab, Cry3Ae or Cry3Bb        or insecticidal portions thereof; or-   2) a crystal protein from Bacillus thuringiensis or a portion    thereof which is insecticidal in the presence of a second other    crystal protein from Bacillus thuringiensis or a portion thereof,    such as the binary toxin made up of the Cy34 and Cy35 crystal    proteins; or-   3) a hybrid insecticidal protein comprising parts of two different    insecticidal crystal proteins from Bacillus thuringiensis, such as a    hybrid of the proteins of 1) above or a hybrid of the proteins of 2)    above, for example the Cry1A.105 protein produced by maize event    MON98034 (WO 2007/027777); or-   4) a protein of any one of points 1) to 3) above wherein some,    particularly 1 to 10, amino acids have been replaced by another    amino acid to obtain a higher insecticidal activity to a target    insect species, and/or to expand the range of target insect species    affected, and/or because of changes induced in the encoding DNA    during cloning or transformation, such as the Cry3Bbl protein in    maize events MON863 or MON88017, or the Cry3A protein in maize event    MIR 604;-   5) an insecticidal secreted protein from Bacillus thuringiensis or    Bacillus cereus, or an insecticidal portion thereof, such as the    vegetative insecticidal proteins (VIP) listed at:    http://www.lifesci.sussex.ac.uk/home/Neil_Crickmore/Bt/vip.html, for    example proteins from the VIP3Aa protein class; or-   6) a secreted protein from Bacillus thuringiensis or Bacillus cereus    which is insecticidal in the presence of a second secreted protein    from Bacillus thuringiensis or B. cereus, such as the binary toxin    made up of the VIP1A and VIP2A proteins;-   7) a hybrid insecticidal protein comprising parts from different    secreted proteins from Bacillus thuringiensis or Bacillus cereus,    such as a hybrid of the proteins in 1) above or a hybrid of the    proteins in 2) above; or-   8) a protein of any one of points 1) to 3) above wherein some,    particularly 1 to 10, amino acids have been replaced by another    amino acid to obtain a higher insecticidal activity to a target    insect species, and/or to expand the range of target insect species    affected, and/or because of changes induced in the encoding DNA    during cloning or transformation (while still encoding an    insecticidal protein), such as the VIP3Aa protein in cotton event    COT 102.

Of course, insect-resistant transgenic plants, as used herein, alsoinclude any plant comprising a combination of genes encoding theproteins of any one of the above classes 1 to 8. In one embodiment, aninsect-resistant plant contains more than one transgene encoding aprotein of any one of the above classes 1 to 8, to expand the range oftarget insect species affected or to delay insect resistance developmentto the plants, by using different proteins insecticidal to the sametarget insect species but having a different mode of action, such asbinding to different receptor binding sites in the insect.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are tolerant to abiotic stress factors. Such plants can beobtained by genetic transformation, or by selection of plants containinga mutation imparting such stress resistance. Particularly usefulstress-tolerant plants include the following:

-   a. plants which contain a transgene capable of reducing the    expression and/or the activity of the poly(ADP-ribose)polymerase    (PARP) gene in the plant cells or plants;-   b. plants which contain a stress tolerance-enhancing transgene    capable of reducing the expression and/or the activity of the    PARC-encoding genes of the plants or plant cells;-   c. plants which contain a stress tolerance-enhancing transgene    coding for a plant-functional enzyme of the nicotinamide adenine    dinucleotide salvage biosynthesis pathway, including nicotinamidase,    nicotinate phosphoribosyltransferase, nicotinic acid mononucleotide    adenyltransferase, nicotinamide adenine dinucleotide synthetase or    nicotinamide phosphoribosyltransferase.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention show altered quantity, quality and/or storage stability of theharvested product and/or altered properties of specific ingredients ofthe harvested product such as, for example:

-   1) Transgenic plants which synthesize a modified starch which is    altered with respect to its chemophysical traits, in particular the    amylose content or the amylose/amylopectin ratio, the degree of    branching, the average chain length, the distribution of the side    chains, the viscosity behaviour, the gel resistance, the grain size    and/or grain morphology of the starch in comparison to the    synthesized starch in wild-type plant cells or plants, such that    this modified starch is better suited for certain applications.-   2) Transgenic plants which synthesize non-starch carbohydrate    polymers or which synthesize non-starch carbohydrate polymers with    altered properties in comparison to wild-type plants without genetic    modification. Examples are plants which produce polyfructose,    especially of the inulin and levan type, plants which produce    alpha-1,4-glucans, plants which produce alpha-1,6-branched    alpha-1,4-glucans, and plants producing alternan.-   3) Transgenic plants which produce hyaluronan.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are plants, such as cotton plants, with altered fibrecharacteristics. Such plants can be obtained by genetic transformation,or by selection of plants containing a mutation imparting such alteredfibre characteristics and include:

-   a) plants, such as cotton plants, which contain an altered form of    cellulose synthase genes;-   b) plants, such as cotton plants, which contain an altered form of    rsw2 or rsw3 homologous nucleic acids;-   c) plants, such as cotton plants, with an increased expression of    sucrose phosphate synthase;-   d) plants, such as cotton plants, with an increased expression of    sucrose synthase;-   e) plants, such as cotton plants, wherein the timing of the    plasmodesmatal gating at the base of the fibre cell is altered, for    example through downregulation of fibre-selective (3-1,3-glucanase;-   f) plants, such as cotton plants, which have fibres with altered    reactivity, for example through the expression of the    N-acetylglucosaminetransferase gene including nodC and chitin    synthase genes.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are plants, such as oilseed rape or related Brassica plants,with altered oil profile characteristics. Such plants can be obtained bygenetic transformation or by selection of plants containing a mutationimparting such altered oil characteristics and include:

-   a) plants, such as oilseed rape plants, which produce oil having a    high oleic acid content;-   b) plants, such as oilseed rape plants, which produce oil having a    low linolenic acid content;-   c) plants, such as oilseed rape plants, which produce oil having a    low level of saturated fatty acids.

Particularly useful transgenic plants which may be treated according tothe invention are plants which comprise one or more genes which encodeone or more toxins and are the transgenic plants available under thefollowing trade names: YIELD GARD® (for example maize, cotton, soyabeans), KnockOut® (for example maize), BiteGard® (for example maize),BT-Xtra® (for example maize), StarLink® (for example maize), Bollgard®(cotton), Nucota® (cotton), Nucotn 33B® (cotton), NatureGard® (forexample maize), Protecta® and NewLeaf® (potato). Examples ofherbicide-tolerant plants which may be mentioned are maize varieties,cotton varieties and soya bean varieties which are available under thefollowing trade names: Roundup Ready® (tolerance to glyphosate, forexample maize, cotton, soya beans), Liberty Link® (tolerance tophosphinothricin, for example oilseed rape), IMI® (tolerance toimidazolinone) and SCS® (tolerance to sulphonylurea, for example maize).Herbicide-resistant plants (plants bred in a conventional manner forherbicide tolerance) which may be mentioned include the varieties soldunder the name Clearfield® (for example maize).

Particularly useful transgenic plants which may be treated according tothe invention are plants containing transformation events, or acombination of transformation events, and that are listed for example inthe databases for various national or regional regulatory agencies (seefor example http://gmoinfo.jrc.it/gmp_browse.aspx andhttp://www.agbios.com/dbase.php).

Moreover, in the protection of materials, the active compounds orcompositions according to the invention can be employed for protectingindustrial materials against attack and destruction by unwantedmicroorganisms, such as, for example, fungi.

Industrial materials in the present context are understood as meaningnon-living materials which have been prepared for use in industry. Forexample, industrial materials which are intended to be protected byactive compounds according to the invention from fungal change ordestruction can be adhesives, sizes, paper, wallpaper, and board,textiles, carpets, leather, wood, paints and plastic articles, coolinglubricants and other materials which can be infected with, or destroyedby, microorganisms. Parts of production plants and buildings, forexample cooling-water circuits, cooling and heating systems andventilation and air-conditioning units, which may be impaired by theproliferation of microorganisms may also be mentioned within the scopeof the materials to be protected. Industrial materials which may bementioned within the scope of the present invention are preferablyadhesives, sizes, paper and board, leather, wood, paints, coolinglubricants and heat-transfer liquids, particularly preferably wood. Theactive compounds or compositions according to the invention may preventdisadvantageous effects, such as rotting, decay, discoloration,decoloration or formation of mould. Moreover, the compounds according tothe invention can be employed for protecting objects which come intocontact with saltwater or brackish water, in particular hulls, screens,nets, buildings, moorings and signalling systems, against fouling.

The method according to the invention for controlling unwanted fungi canalso be employed for protecting storage goods. Here, storage goods areto be understood as meaning natural substances of vegetable or animalorigin or processed products thereof of natural origin, for whichlong-term protection is desired. Storage goods of vegetable origin, suchas, for example, plants or plant parts, such as stems, leaves, tubers,seeds, fruits, grains, can be protected freshly harvested or afterprocessing by (pre)drying, moistening, comminuting, grinding, pressingor roasting. Storage goods also include timber, both unprocessed, suchas construction timber, electricity poles and barriers, or in the formof finished products, such as furniture. Storage goods of animal originare, for example, hides, leather, furs and hairs. The active compoundsaccording to the invention may prevent disadvantageous effects, such asrotting, decay, discoloration, decoloration or formation of mould.

Some pathogens of fungal diseases which can be treated according to theinvention may be mentioned by way of example, but not by way oflimitation:

diseases caused by powdery mildew pathogens, such as, for example,Blumeria species, such as, for example, Blumeria graminis; Podosphaeraspecies, such as, for example, Podosphaera leucotricha; Sphaerothecaspecies, such as, for example, Sphaerotheca fuliginea; Uncinula species,such as, for example, Uncinula necator; diseases caused by rust diseasepathogens, such as, for example, Gymnosporangium species, such as, forexample, Gymnosporangium sabinae; Hemileia species, such as, forexample, Hemileia vastatrix; Phakopsora species, such as, for example,Phakopsora pachyrhizi and Phakopsora meibomiae; Puccinia species, suchas, for example, Puccinia recondita or Puccinia triticina; Uromycesspecies, such as, for example, Uromyces appendiculatus;

diseases caused by pathogens from the group of the Oomycetes, such as,for example, Bremia species, such as, for example, Bremia lactucae;Peronospora species, such as, for example, Peronospora pili or P.brassicae; Phytophthora species, such as, for example, Phytophthorainfestans; Plasmopara species, such as, for example, Plasmoparaviticola; Pseudoperonospora species, such as, for example,Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species,such as, for example, Pythium ultimum;

leaf blotch diseases and leaf wilt diseases caused, for example, byAlternaria species, such as, for example, Alternaria solani; Cercosporaspecies, such as, for example, Cercospora beticola; Cladiosporiumspecies, such as, for example, Cladiosporium cucumerinum; Cochliobolusspecies, such as, for example, Cochliobolus sativus (conidia form:Drechslera, syn: Helminthosporium); Colletotrichum species, such as, forexample, Colletotrichum lindemuthanium; Cycloconium species, such as,for example, Cycloconium oleaginum; Diaporthe species, such as, forexample, Diaporthe citri; Elsinoe species, such as, for example, Elsinoefawcettii; Gloeosporium species, such as, for example, Gloeosporiumlaeticolor; Glomerella species, such as, for example, Glomerellacingulate; Guignardia species, such as, for example, Guignardiabidwelli; Leptosphaeria species, such as, for example, Leptosphaeriamaculans; Magnaporthe species, such as, for example, Magnaporthe grisea;Microdochium species, such as, for example, Microdochium nivale;Mycosphaerella species, such as, for example, Mycosphaerella graminicolaand M. fijiensis; Phaeosphaeria species, such as, for example,Phaeosphaeria nodorum; Pyrenophora species, such as, for example,Pyrenophora teres; Ramularia species, such as, for example, Ramulariacollocygni; Rhynchosporium species, such as, for example, Rhynchosporiumsecalis; Septoria species, such as, for example, Septoria apii; Typhulaspecies, such as, for example, Typhula incarnata; Venturia species, suchas, for example, Venturia iraequalis;

root and stem diseases caused, for example, by Corticium species, suchas, for example, Corticium graminearum; Fusarium species, such as, forexample, Fusarium oxysporum; Gaeumannomyces species, such as, forexample, Gaeumannomyces graminis; Rhizoctonia species, such as, forexample Rhizoctonia solani; Tapesia species, such as, for example,Tapesia acuformis; Thielaviopsis species, such as, for example,Thielaviopsis basicola;

ear and panicle diseases (including corn cobs) caused, for example, byAlternaria species, such as, for example, Alternaria spp.; Aspergillusspecies, such as, for example, Aspergillus flavus; Cladosporium species,such as, for example, Cladosporium cladosporioides; Claviceps species,such as, for example, Claviceps purpurea; Fusarium species, such as, forexample, Fusarium culmorum; Gibberella species, such as, for example,Gibberella zeae; Monographella species, such as, for example,Monographella nivalis; Septoria species, such as, for example, Septorianodorum;

diseases caused by smut fungi, such as, for example, Sphacelothecaspecies, such as, for example, Sphacelotheca reiliana; Tilletia species,such as, for example, Tilletia caries, T. controversa; Urocystisspecies, such as, for example, Urocystis occulta; Ustilago species, suchas, for example, Ustilago nuda, U. nuda tritici;

fruit rot caused, for example, by Aspergillus species, such as, forexample, Aspergillus flavus; Botrytis species, such as, for example,Botrytis cinerea; Penicillium species, such as, for example, Penicilliumexpansum and P. purpurogenum; Sclerotinia species, such as, for example,Sclerotinia sclerotiorum;

Verticilium species, such as, for example, Verticilium alboatrum;

seed- and soil-borne rot and wilt diseases, and also diseases ofseedlings, caused, for example, by Fusarium species, such as, forexample, Fusarium culmorum; Phytophthora species, such as, for example,Phytophthora cactorum; Pythium species, such as, for example, Pythiumultimum; Rhizoctonia species, such as, for example, Rhizoctonia solani;Sclerotium species, such as, for example, Sclerotium rolfsii;

cancerous diseases, galls and witches' broom caused, for example, byNectria species, such as, for example, Nectria galligena;

wilt diseases caused, for example, by Monilinia species, such as, forexample, Monilinia laxa;

deformations of leaves, flowers and fruits caused, for example, byTaphrina species, such as, for example, Taphrina deformans;

degenerative diseases of woody plants caused, for example, by Escaspecies, such as, for example, Phaeomoniella chlamydospora andPhaeoacremonium aleophilum and Fomitiporia mediterranea;

diseases of flowers and seeds caused, for example, by Botrytis species,such as, for example, Botrytis cinerea;

diseases of plant tubers caused, for example, by Rhizoctonia species,such as, for example, Rhizoctonia solani; Helminthosporium species, suchas, for example, Helminthosporium solani;

diseases caused by bacterial pathogens, such as, for example,Xanthomonas species, such as, for example, Xanthomonas campestris pv.oryzae; Pseudomonas species, such as, for example, Pseudomonas syringaepv. lachrymans; Erwinia species, such as, for example, Erwiniaamylovora.

Preference is given to controlling the following diseases of soya beans:

Fungal diseases on leaves, stems, pods and seeds caused, for example, byalternaria leaf spot (Alternaria spec. atrans tenuissima), anthracnose(Colletotrichum gloeosporoides dematium var. truncatum), brown spot(Septoria glycines), cercospora leaf spot and blight (Cercosporakikuchii), choanephora leaf blight (Choanephora infundibulifera trispora(Syn.)), dactuliophora leaf spot (Dactuliophora glycines), downy mildew(Peronospora manshurica), drechslera blight (Drechslera glycini),frogeye leaf spot (Cercospora sojina), leptosphaerulina leaf spot(Leptosphaerulina trifolii), phyllostica leaf spot (Phyllostictasojaecola), pod and stem blight (Phomopsis sojae), powdery mildew(Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines),rhizoctonia aerial, foliage, and web blight (Rhizoctonia solani), rust(Phakopsora pachyrhizi, Phakopsora meibomiae), scab (Sphacelomaglycines), stemphylium leaf blight (Stemphylium botryosum), target spot(Corynespora cassiicola).

Fungal diseases on roots and the stem base caused, for example, by blackroot rot (Calonectria crotalariae), charcoal rot (Macrophominaphaseolina), fusarium blight or wilt, root rot, and pod and collar rot(Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusariumequiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris),neocosmospora (Neocosmospora vasinfecta), pod and stem blight (Diaporthephaseolorum), stem canker (Diaporthe phaseolorum var. caulivora),phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophoragregata), pythium rot (Pythium aphanidermatum, Pythium irregulare,Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctoniaroot rot, stem decay, and damping-off (Rhizoctonia solani), sclerotiniastem decay (Sclerotinia sclerotiorum), sclerotinia southern blight(Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).

Organisms which can bring about degradation or modification of theindustrial materials and which may be mentioned are fungi. The activecompounds according to the invention preferably act against fungi, inparticular moulds, wood-discolouring and wood-destroying fungi(Basidiomycetes). Fungi of the following genera may be mentioned asexamples: Alternaria, such as Alternaria tennis; Aspergillus, such asAspergillus niger; Chaetomium, such as Chaetomium globosum; Coniophora,such as Coniophora puetana; Lentinus, such as Lentinus tigrinus;Penicillium, such as Penicillium glaucum; Polyporus, such as Polyporusversicolor; Aureobasidium, such as Aureobasidium pullulans; Sclerophoma,such as Sclerophoma pityophila; Trichoderma, such as Trichoderma viride.

In addition, the active compounds according to the invention also havevery good antimycotic activity. They have a very broad antimycoticactivity spectrum, in particular against dermatophytes and yeasts,moulds and diphasic fungi, (for example against Candida species, such asCandida albicans, Candida glabrata), and Epidermophyton floccosum,Aspergillus species, such as Aspergillus niger and Aspergillusfumigatus, Trichophyton species, such as Trichophyton mentagrophytes,Microsporon species such as Microsporon canis and audouinii. The list ofthese fungi by no means limits the mycotic spectrum covered, but is onlyfor illustration.

When using the active compounds according to the invention asfungicides, the application rates can be varied within a relatively widerange, depending on the kind of application. The application rate of theactive compounds according to the invention is

when treating plant parts, for example leaves: from 0.1 to 10 000 g/ha,preferably from 10 to 1000 g/ha, particularly preferably from 50 to 300g/ha (when the application is carried out by watering or dripping, it iseven possible to reduce the application rate, especially when inertsubstrates such as rock wool or perlite are used);

when treating seed: from 2 to 200 g per 100 kg of seed, preferably from3 to 150 g per 100 kg of seed, particularly preferably from 2.5 to 25 gper 100 kg of seed, very particularly preferably from 2.5 to 12.5 g per100 kg of seed;

when treating the soil: from 0.1 to 10 000 g/ha, preferably from 1 to5000 g/ha.

These application rates are mentioned only by way of example and are notlimiting in the sense of the invention.

The active compounds or compositions according to the invention can thusbe employed for protecting plants for a certain period of time aftertreatment against attack by the pathogens mentioned. The period forwhich protection is provided extends generally for 1 to 28 days,preferably for 1 to 14 days, particularly preferably for 1 to 10 days,very particularly preferably for 1 to 7 days after the treatment of theplants with the active compounds, or for up to 200 days after a seedtreatment.

In addition, by the treatment according to the invention it is possibleto reduce the mycotoxin content in the harvested material and thefoodstuffs and feedstuffs prepared therefrom. Particular, but notexclusive, mention may be made here of the following mycotoxins:deoxynivalenol (DON), nivalenol, 15-Ac-DON, 3-Ac-DON, T2- and HT2-toxin,fumonisins, zearalenon, moniliformin, fusarin, diaceotoxyscirpenol(DAS), beauvericin, enniatin, fusaroproliferin, fusarenol, ochratoxins,patulin, ergot alkaloids and aflatoxins produced, for example, by thefollowing fungi: Fusarium spec., such as Fusarium acuminatum, F.avenaceum, F. crookwellense, F. culmorurn, F. graminearum (Gibberellazeae), F. equiseti, F. fujikoroi, F. musarum, F. oxysporum, F.proliferatum, F. poae, F. pseudograminearum, F. sambucinum, F. scirpi,F. semitectum, F. solani, F. sporotrichoides, F. langsethiae, F.subglutinans, F. tricinctum, F. verticillioides, inter alia, and also byAspergillus spec., Penicillium spec., Claviceps purpurea, Stachybotrysspec., inter alia.

The plants listed can be treated according to the invention in aparticularly advantageous manner with the ketoheteroarylpiperidine and-piperazine derivatives of the formula (I) or the compositions accordingto the invention. The preferred ranges stated above for the activecompounds or compositions also apply to the treatment of these plants.Particular emphasis is given to the treatment of plants with thecompounds or compositions specifically mentioned in the present text.

The preparation and the use of the active compounds of the formula (I)according to the invention is illustrated by the examples below.However, the invention is not limited to these examples.

General Note: Unless indicated otherwise, all chromatographicpurification and separation steps are carried out on silica gel andusing a solvent gradient of from 0:100 ethyl acetate/cyclohexane to100:0 ethyl acetate/cyclohexane.

EXAMPLES

Preparation of (I-24):

Step 1

tert-Butyl4-{4-[methoxy(methyl)carbamoyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(V-1)

At room temperature, triethylamine (324 mg) was added to a suspension of2-[1-(tert-butoxycarbonyl)piperidin-4-yl]-1,3-thiazole-4-carboxylic acid(1.0 g) in dichloromethane (30 mL). After ten minutes of stirring,methoxy(methyl)ammonium chloride (312 mg), 4-dimethylaminopyridine (39mg) and 1-ethyl-3-(3′-dimethylaminopropyl)carbodiimide HCl salt (675 mg)were added. The mixture was stirred at room temperature overnight, andwater was then added. The aqueous phase was separated off and extractedwith ethyl acetate. The combined organic phases are dried over sodiumsulphate and concentrated under reduced pressure. The residue waspurified chromatographically. This gave tert-butyl4-{4-[methoxy(methyl)carbamoyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(1.0 g).

log P (pH 2.7): 2.40

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.41 (s, 9H), 1.52-1.63 (m, 2H),2.02-2.08 (m, 2H), 2.90 (bs, 2H), 3.19-3.30 (1H), 3.29 (s, 3H), 3.32 (s,3H), 3.96-4.04 (m, 2H), 8.09 (s, 1H)

MS (ESI): 356 ([M+H]⁺)

Step 2

tert-Butyl4-[4-(cyclohexylacetyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate (IV-1)

Under argon and at −78° C., cyclohexylmethylmagnesium chloride 0.5M indiethyl ether (2.7 ml) was added dropwise to a solution of tert-butyl4-{4-[methoxy(methyl)carbamoyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(480 mg) in tetrahydrofuran (5 ml). The reaction mixture was stirred at−78° C. for one hour. The reaction mixture was then stirred at roomtemperature for one hour. Saturated ammonium chloride solution was thenadded to the reaction mixture, and the aqueous phase was separated off.After extraction of the aqueous phase with ethyl acetate, the combinedorganic phases were dried over sodium sulphate and the solvent wasremoved under reduced pressure. This gave tert-butyl4-[4-(cyclohexylacetyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate (335mg).

log P (pH 2.7): 5.43

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 0.98-1.05 (m, 2H), 1.14-1.22 (m,1H), 1.22-1.31 (m, 2H), 1.44 (s, 9H), 1.61-1.76 (m, 8H), 2.05-2.10 (m,2H). 2.87 (d, 2H), 2.90 (bs, al), 3.18-3.26 (m, 1H), 4.07-4.15 (m, 2H),8.10 (s, 1H)

MS (ESI): 337 ([M−(CH₃)₃C+H]⁺)

Step 3

4-[4-(Cyclohexylacetyl)-1,3-thiazol-2-yl]piperidinium chloride (II-1)

Under argon and at 0° C., a solution of hydrogen chloride in dioxane(4M, 1 ml) was added to a solution of tert-butyl4-[4-(cyclohexylacetyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate (5.0g) in diethyl ether (1 ml). The mixture was stirred at 0° C. and thenslowly warmed to room temperature. After stirring overnight, excess acidand the solvent were removed under reduced pressure. This gave4[4-(cyclohexylacetyl)-1,3-thiazol-2-yl]piperidinium chloride (315 mg).

log P (pH 2.7): 1.35

MS (ESI): 293 ([M−Cl]⁺)

Step 4

2-[3,5-Bis(difluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(cyclohexylacetyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(I-24)

Oxalyl chloride (116 mg) and a drop of N,N-dimethylformamide were addedto a solution of [3,5-(difluoromethyl)-1H-pyrazol-1-yl]acetic acid (69mg) in dichloromethane (5 ml). The reaction mixture was then stirred for30 minutes. Excess oxalyl chloride was then removed under reducedpressure, and the residue was redissolved in dichloromethane (2 ml). Thesolution was then added to a solution of4-[4-(cyclohexylacetyl)-1,3-thiazol-2-yl]piperidinium chloride (100 mg)in dichloromethane (5 ml) and triethylamine (92 mg). The reactionmixture was stirred for 30 minutes. Solvent and triethylamine wereremoved under reduced pressure. Purification of the residue by columnchromatography gave2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(cyclohexylacetyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(105 mg).

log P (pH 2.7): 4.02

¹H NMR (DMSO-d₆, 400 MHz): 0.95-1.02 (m, 2H), 1.10-1.26 (m, 3H),1.54-1.69 (m, 6H), 1.77-1.91 (m, 2H), 2.06-2.15 (m, 2H), 2.82-2.87 (m,1H), 2.89 (d, 2H), 3.25-3.30 (m, 1H), 3.35-3.41 (m, 1H), 3.94-3.99 (m,1H), 4.33-4.37 (m, 1H), 5.36 (d, 1H), 5.45 (d, 1H), 6.91 (s, 1H), 7.04(t, 1H), 7.18 (t, 1H), 8.44 (s, 1H)

MS (ESI): 501 ([M+H]⁺)

Preparation of Compound (I-25)

Step 1

N-(5-Chloro-2-methylphenyl)-4-[4-(cyclohexylacetyl)-1,3-thiazol-2-yl]piperidine-1-carboxamide(I-25)

Triethylamine (0.047 ml) was added to a mixture of4-[4-(cyclohexylacetyl)-1,3-thiazol-2-yl]piperidinium chloride (100 mg)in dichloromethane (1 ml). After the solid had dissolved completely,4-chloro-2-isocyanato-1-methylbenzene (51 mg) and a drop of1,8-diazabicyclo[5.4.0]undec-7-ene were added. The reaction mixture wasthen stirred for 5 minutes.

Solvent and triethylamine were removed under reduced pressure.Purification of the residue by column chromatography gaveN-(5-chloro-2-methylphenyl)-4-[4-(cyclohexylacetyl)-1,3-thiazol-2-yl]piperidine-1-carboxamide(128 mg).

log P (pH 2.7): 4.51

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 0.94-1.05 (m, 2H), 1.10-1.26 (m,4H), 1.56-1.73 (m, 6H), 1.83-1.92 (m, 1H), 2.06-2.13 (m, 2H), 2.16 (s,3H), 2.88 (d, 2H), 2.98-3.06 (m, 2H), 3.30-3.38 (m, 1H), 4.11-4.18 (m,2H), 7.07 (dd, 1H), 7.19 (d, 1H), 7.33 (d, 1H), 8.12 (s, 1H), 8.04 (s,1H)

MS (ESI): 460 ([M+H]⁺)

Preparation of Compound (I-58)

Step 1

1-[2-(1-{2-[3,5-Bis(difluoromethyl)-1H-pyrazol-1-yl]ethanethioyl}piperidin-4-yl)-1,3-thiazol-4-yl]-2-cyclohexylethanone(I-58)

At room temperature,2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide (194mg) was added to a solution of2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(cyclohexylacetyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(200 mg) in toluene (2 ml). The reaction mixture was stirred at 60° C.for 2 hours. After removal of the solvent under reduced pressure, theresidue was purified chromatographically. This gave1-[2-(1-{2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]ethanethioyl}-piperidin-4-yl)-1,3-thiazol-4-yl]-2-cyclohexylethanone(101 mg, 49%).

log P (pH 2.7): 4.63

1H NMR (DMSO-d₅, 400 MHz): δ_(ppm): 0.94-1.05 (m, 2H), 1.10-1.30 (m,4H), 1.56-1.80 (m, 6H), 1.83-1.95 (m, 1H), 2.06-2.15 (m, 2H), 2.88 (d,2H), 3.30-3.42 (m, 1H), 3.51-3.61 (m, 2H), 4.42-4.49 (m, 1H), 5.26-5.33(m, 1H), 5.55 (d, 1H), 5.59 (d, 1H), 6.89 (s, 1H), 7.02 (t, 1H), 7.20(t, 1H), 8.04 (s, 1H)

MS (ESI): 517 ([M+H]⁺)

Preparation of Compound (I-60)

Step 1

tert-Butyl4-[4-(2-cyclohexyl-N-methoxyethanimidoyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate

At room temperature, methoxyammonium chloride (171 mg) was added to asolution of tert-butyl4-{4-[methoxy(methyl)carbamoyl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(403 mg) in ethanol (2 ml). The reaction mixture was stirred at 50° C.for 24 hours, and water was then added. The aqueous phase was separatedoff and extracted with ethyl acetate. The combined organic phases weredried over sodium sulphate and concentrated under reduced pressure. Theresidue was purified chromatographically. This gave tert-butyl4-[4-(2-cyclohexyl-N-methoxyethanimidoyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate(361 mg).

Step 2

2-[3,5-Bis(difluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(2-cyclohexyl-N-methoxyethanimidoyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(I-60)

Under argon and at 0° C., a solution of hydrogen chloride in dioxane(4M, 2.6 ml) was added to a suspension of tert-butyl4-[4-(2-cyclohexyl-N-methoxyethanimidoyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate(287 mg). The mixture was stirred at 0° C. and then slowly warmed toroom temperature. After stirring overnight, excess acid and the solventwere removed under reduced pressure. This gave4-[4-(2-cyclohexyl-N-methoxyethanimidoyl)-1,3-thiazol-2-yl]piperidiniumchloride.

At room temperature, [3,5-(difluoromethyl)-1H-pyrazol-1-yl]acetic acid(225 mg), dimethylaminopyridine (12 mg) and1-ethyl-3-(3′-dimethylaminopropyl)carbodiimide (89 mg) were added to asolution of4-[4-(2-cyclohexyl-N-methoxyethanimidoyl)-1,3-thiazol-2-yl]piperidiniumchloride (357 mg) in dichloromethane (3 ml) and triethylamine (101 mg).The mixture was stirred for 3 hours, and water was then added. Theaqueous phase was removed and extracted with ethyl acetate. The combinedorganic phases were dried with sodium sulphate. The solid was filteredoff and the solvent was distilled off. The residue was purifiedchromatographically. This gave2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-{4-[4-(2-cyclohexyl-N-methoxyethanimidoyl)-1,3-thiazol-2-yl]piperidin-1-yl}ethanone(182 mg, 70%).

log P (pH 2.7): 4.80

MS (ESI): 530 ([M+H]⁺)

Preparation of compound (I-14)

Step 1

tert-Butyl4-[4-(1-hydroxy-3-phenylpropyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate(XVI-1)

Under an argon atmosphere and at −78° C., chloro(2-phenylethyl)magnesium(1M in diethyl ether, 3.77 ml) was added dropwise to a solution oftert-butyl 4-(4-formyl-1,3-thiazol-2-yl)piperidine-1-carboxylate (1.0 g)in tetrahydrofuran (10 ml). The reaction mixture was stirred at −78° C.for one hour, and more chloro(2-phenylethyl)magnesium (3M in diethylether, 0.20 ml) was then added dropwise. The reaction mixture was thenstirred for 20 minutes. Saturated ammonium chloride solution was thenadded to the reaction mixture, and the aqueous phase was separated off.After extraction of the aqueous phase with ethyl acetate, the combinedorganic phases were dried over sodium sulphate and the solvent wasremoved under reduced pressure. This gave tert-butyl4-[4-(1-hydroxy-3-phenylpropyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate(790 mg).

log P (pH 2.7): 3.79

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.41 (s, 9H), 1.48-1.61 (m, 2H),1.90-2.11 (4H), 2.62-2.67 (m, 2H), 2.87-2.95 (m, 2H), 3.15-3.20 (m, 1H),3.94-4.00 (2H), 4.62-4.67 (m, 1H), 5.09-5.12 (m, 1H), 7.11-7.18 (m, 3H),7.22-7.27 (m, 3H)

MS (ESI): 347 ([M−C(CH₃)₃+2H]⁺)

Step 2

tert-Butyl4-[4-(3-phenylpropanoyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate(IV-2)

At room temperature, 1,1,1-triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-one (15% strength solution indichloromethane, 8.3 g) was added dropwise to a solution of tert-butyl4-[4-(1-hydroxy-3-phenylpropyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate(790 mg) in dichloromethane (7.9 ml). The reaction mixture was stirredat room temperature overnight. 5 g of silica gel were then added, andthe solvent was removed under reduced pressure. The residue was purifiedchromatographically. This gave tert-butyl4-[4-(3-phenylpropanoyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate (545mg).

log P (pH 2.7): 4.54

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.41 (s, 9H), 1.54-1.65 (m, 2H),2.00-2.08 (m, 2H), 2.88-2.97 (m, 4H), 3.20-3.30 (m, 1H), 3.31 (t, 2H),3.96-4.02 (m, 2H), 7.12-7.18 (m, 1H), 7.21-7.28 (m, 4H), 8.35 (s, 1H)

MS (EST): 345 ([M−C(CH₃)₃+2H]⁺)

Step 3

4-[4-(3-Phenylpropanoyl)-1,3-thiazol-2-yl]piperidinium chloride (II-2)

tert-Butyl4-[4-(3-phenylpropanoyl)-1,3-thiazol-2-yl]piperidine-1-carboxylate (550mg) was reacted analogously to II-1 (step 3) with hydrogen chloride indiethyl ether (2M, 11 ml). This gave4-[4-(3-phenylpropanoyl)-1,3-thiazol-2-yl]piperidinium chloride (500mg).

log P (pH 2.7): 1.19

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.95-2.05 (m, 2H), 2.18-2.25 (m,2H), 2.96 (t, 2H), 3.00-3.08 (m, 2H), 3.29-3.36 (m, 4H), 3.36-3.46 (m,1H), 7.13-7.18 (m, 1H), 7.22-7.30 (m, 4H), 8.40 (s, 1H), 8.99 (bs, 1H),9.22 (bs, 1H)

MS (ESI): 301 ([M−Cl]⁺)

Step 4

1-[2-(1-{[5-Methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-3-phenylpropan-1-one

4-[4-(3-Phenylpropanoyl)-1,3-thiazol-2-yl]piperidinium chloride (502 mg)was reacted analogously to I-24 (step 4) with[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetic acid (310 mg). Thisgave 1-[2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-3-phenylpropan-1-one(495 mg).

log P (pH 2.7): 3.64

¹H NMR (DMSO-d₅, 400 MHz): δ_(ppm): 1.65 (bs, 1H), 1.80 (bs, 1H),2.08-2.17 (m, 2H), 2.22 (s, 3H), 2.90 (bs, 1H), 2.96 (t, 2H), 3.20-3.42(m, 2H), 3.33 (t, 2H), 3.99 (bs, 1H), 4.33 (bs, 1H), 5.15-5.25 (m, 2H),6.44 (s, 1H), 7.14-7.18 (m, 1H), 7.21-7.30 (m, 4H), 8.37 (s, 1H)

MS (EST): 491 ([M+H])

Preparation of Compound (I-12)

Step 1

1-[2-(Piperidin-4-yl)-1,3-thiazol-4-yl]ethanone hydrochloride

Under an argon atmosphere and at 0° C., hydrochloric acid (2 M indiethyl ether, 23 ml) was added dropwise to a solution of tert-butyl4-(4-acetyl-1,3-thiazol-2-yl)piperidine-1-carboxylate (920 mg) indiethyl ether (2 ml). The reaction mixture was stirred for 24 hours.Solvent and excess acid were removed under reduced pressure. This gave1[2-(piperidin-4-yl)-1,3-thiazol-4-yl]ethanone hydrochloride (1.05 g) asa white highly hygroscopic solid which was immediately processedfurther.

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 2.01 (qd, 2H), 2.28-2.20 (m, 2H),2.55 (s, 3H), 3.02 (q, 2H), 3.38-3.27 (m, 2H), 3.42 (m, 1H), 8.39 (s,1H), 9.06 (bs, 1H), 9.25 (bs, 1H)

MS (ESI): 211 ([M+H-Cl]⁺)

Step 2

1-[4-(4-Acetyl-1,3-thiazol-2-yl)piperidin-1-yl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone(XXII-1)

Oxalyl chloride (1.74 g) and a drop of N,N-dimethylformamide were addedto a solution of [5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]aceticacid (1.00 g) in dichloromethane (10 ml). The reaction mixture was thenstirred for 24 hours. Excess oxalyl chloride was then removed underreduced pressure, and the residue was redissolved in dichloromethane (10ml). With cooling on an ice bath, the solution was then added to asuspension of 1-[2-(piperidin-4-yl)-1,3-thiazol-4-yl]ethanonehydrochloride (1.13 g) in dichloromethane (10 ml) andN,N-diisopropylethylamine (1.77 g). The reaction mixture was thenallowed to warm to room temperature and stirred for another 2 hours.Saturated aqueous ammonium chloride solution (5 ml) was then added tothe reaction mixture. The aqueous phase was separated off and extractedwith dichloromethane. All organic phases were combined and dried withanhydrous sodium sulphate. The solid was then filtered off and thesolvent was removed under reduced pressure. Purification by columnchromatography (silica gel, ethyl acetate:hexane 0%-100% elutiongradient) gave1-[4-(4-acetyl-1,3-thiazol-2-yl)piperidin-1-yl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone(1.00 g).

log P (pH 2.7): 2.25

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.65 (bs, 1H), 1.80 (bs, 1H),2.18-2.11 (m, 2H), 2.23 (s, 3H), 2.55 (s, 3H), 2.90 (bs, 1H), 3.28 (bs,1H), 3.39 (m, 1H), 4.00 (bs, 1H), 4.33 (bs, 1H), 5.22 (bs, 2H), 6.45 (s,1H), 8.36 (s, 1H)

MS (ESI): 401 ([M+H]⁺)

Step 3

(2E)-3-(2,6-Difluorophenyl)-1-[2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]prop-2-en-1-one(I-12)

At room temperature, a solution of sodium hydroxide (19 mg) in methanol(0.25 ml) and water (0.05 ml) was added to a solution of1-[4-(4-acetyl-1,3-thiazol-2-yl)piperidin-1-yl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone(190 mg) and 2,6-difluorobenzaldehyde (67 mg) in methanol (0.12 ml). Thereaction mixture was stirred at room temperature overnight. Afteraqueous work-up, the mixture was extracted with ethyl acetate and theextracts were dried with sodium sulphate and concentrated under reducedpressure. The residue was purified chromatographically. This gave(2E)-3-(2,6-difluorophenyl)-1-[2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]prop-2-en-1-one(160 mg).

log P (pH 2.7): 3.83

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.56-1.68 (m, 1H), 1.78-1.91 (m,1H), 2.10-2.21 (m, 2H), 2.22 (s, 3H), 2.84-2.92 (m, 1H), 3.20-3.50 (m,2H), 3.95-4.05 (m, 1H), 4.36-4.92 (m, 1H), 5.23 (d, 1H), 5.34 (d, 1H),6.50 (s, 1H), 7.26 (d, 1H), 7.28 (d, 1H), 7.58 (m, 1H), 7.81 (d, 1H),8.07 (d, 1H), 8.626 (s, 1H)

MS (ESI): 525 ([M+H]⁺)

Preparation of Compound (I-11)

Step 1

tert-Butyl 4-(4-ethynyl-1,3-thiazol-2-yl)piperidine-1-carboxylate (VI-1)

Under argon, tert-butyl4-(4-formyl-1,3-thiazol-2-yl)piperidine-1-carboxylate (600 mg) wasdissolved in methanol, and potassium carbonate (839 mg) and dimethyl1-diazo-2-oxopropylphos-phonate (786 mg) were added. The mixture wasstirred at room temperature for 3 hours. After aqueous work-up, themixture was extracted with ethyl acetate, the extracts were dried withsodium sulphate and the solvent was concentrated under reduced pressure.The residue was purified chromatographically. This gave tert-butyl4-(4-ethynyl-1,3-thiazol-2-yl)piperidine-1-carboxylate (493 mg).

log P (pH 2.7): 3.10

¹H NMR (CD₃CN): δ 7.51 (s, 1H), 4.07 (d, 2H), 3.36 (s, 1H), 3.16 (m,1H), 2.90 (t, 2H), 2.10-2.00 (m, 2H), 1.65 (qd, 2H), 1.43 (s, 9H) ppm

MS (ESI): 237 ([M+2H—C(CH₃)₃]⁺)

Step 2

1-[4-(4-Ethynyl-1,3-thiazol-2-yl)piperidin-1-yl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone(XX-1)

At room temperature, a solution of trifluoroacetic acid (30% indichloromethane, 2 ml) was added to tert-butyl4-(4-ethynyl-1,3-thiazol-2-yl)piperidine-1-carboxylate (100 mg). After30 minutes of stirring, triethylamine (2 ml) was added to the reactionmixture.

Oxalyl chloride (130 mg) and a drop of N,N-dimethylformamide were addedto a solution of [5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]aceticacid (71 mg) in dichloromethane (2 ml). The reaction mixture was thenstirred for 30 minutes. Excess oxalyl chloride was then removed underreduced pressure, and the residue was redissolved in dichloromethane (2ml). The solution was then added to the first solution. The reactionmixture was stirred for 1 hour. Solvent and triethylamine were removedunder reduced pressure, and the residue was then purifiedchromatographically. This gave1-[4-(4-ethynyl-1,3-thiazol-2-yl)piperidin-1-yl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone(130 mg).

log P (pH 2.7): 2.61

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.60 (bs, 1H), 1.76 (bs, 1H),2.05-2.12 (m, 2H), 2.22 (s, 3H), 2.88 (bs, 1H), 3.20-3.35 (m, 2H), 3.98(bs, 1H), 4.08 (s, 1H), 4.32 (bs, 1H), 5.20 (bs, 2H), 6.45 (s, 1H), 7.86(s, 1H)

MS (ESI): 383 ([M+H]⁺)

Step 3

1-(2-Ethoxyphenyl)-3-[2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]prop-2-yn-1-one(I-11)

At room temperature and under an atmosphere of argon, palladium(II)chloride (5.8 mg) and copper(I) iodide were added to a solution of1-[4-(4-ethynyl-1,3-thiazol-2-yl)piperidin-1-yl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone(250 mg) and 2-ethoxybenzoyl chloride in tetrahydrofuran. The mixturewas stirred at room temperature for 1 minute, and triethylamine (83 mg)was then added. The reaction mixture was stirred at room temperatureovernight. 5 g of silica gel were then added, and the solvent wasremoved under reduced pressure. The residue was purifiedchromatographically. This gave1-(2-ethoxyphenyl)-3-[2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]prop-2-yn-1-one(244 mg).

log P (pH 2.7): 3.78

¹H NMR (CD₃CN, 400 MHz): δ_(ppm): 1.44 (t, 3H), 1.65-1.95 (m, 2H),2.12-2.21 (m, 2H), 2.24 (s, 3H), 2.90 (bs, 1H), 3.25-3.38 (m, 2H), 3.95(bs, 1H), 4.22 (q, 2H), 4.43 (1H), 5.04 (bs, 2H), 6.37 (s, 1H),7.02-7.18 (m, 2H), 7.54-7.60 (m, 1H), 7.87 (dd, 1H), 7.89 (s, 1H)

MS (ESI): 531 ([M+H]⁺)

Preparation of Compound (I-20)

Step 1

1-(2-Ethoxyphenyl)-3-[2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]propan-1-one(I-20)

1-(2-Ethoxyphenyl)-3-[2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]prop-2-yn-1-one(130 mg) was dissolved in methanol and hydrogenated at 40° C. and an H₂pressure of 10 bar and in the presence of Pd/C (10%). This gave, afterfiltration and removal of the solvent under reduced pressure,1-(2-ethoxyphenyl)-3-[2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]propan-1-one(40 mg).

log P (pH 2.7): 3.70

¹H NMR (CD₃CN, 400 MHz): δ_(ppm): 1.44 (t, 3H), 1.58-1.70 (m, 1H),1.75-1.86 (m, 1H), 2.06-2.18 (m, 2H), 2.25 (s, 3H), 2.82-2.90 (m, 1H),3.09 (t, 2H), 3.20-3.32 (m, 2H), 3.42 (t, 2H), 3.88-3.95 (m, 1H), 4.16(q, 2H), 4.42-4.47 (m, 1H), 5.04 (d, 1H), 5.11 (d, 1H), 6.42 (s, 1H),6.95 (s, 1H), 7.01 (t, 1H), 7.09 (d, 1H), 7.47-7.53 (m, 1H), 5.59 (dd,1H)

MS (ESI): 535 ([M+H]⁺)

Preparation of Compound (I-22)

Step 1

tert-Butyl4-[4-[(1E)-3-(2,6-difluorophenyl)-3-oxoprop-1-en-1-yl]-1,3-thiazol-2-yl]piperidine-1-carboxylate(IV-3)

tert-Butyl 4-(4-formyl-1,3-thiazol-2-yl)piperidine-1-carboxylate (500mg) was reacted analogously to I-12 (step 3) with1-(2,6-difluorophenyl)ethanone (263 mg). This gave tert-butyl4-{4-[(1E)-3-(2,6-difluorophenyl)-3-oxoprop-1-en-1-yl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(720 mg).

log P (pH 2.7): 4.30 ¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.41 (s, 9H),1.51-1.61 (m, 2H), 2.00-2.08 (m, 2H), 2.90 (bs, 2H), 3.80-4.04 (m, 3H),7.15 (d, 1H), 7.27 (t, 2H), 7.47 (d, 1H), 7.60-7.70 (m, 1H), 8.16 (s,1H)

MS (ESI): 335 ([M−C═OOC(CH₃)₃+2H]⁺)

Step 2

(2E)-3-[2-(1-{[3,5-Bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1-(2,6-difluorophenyl)prop-2-en-1-one(I-22)

tert-Butyl4-{4-[(1E)-3-(2,6-difluorophenyl)-3-oxoprop-1-en-1-yl]-1,3-thiazol-2-yl}piperidine-1-carboxylate(720 mg) was reacted analogously to II-1 (step 3). This gave4-{4-[(1E)-3-(2,6-difluorophenyl)-3-oxoprop-1-en-1-yl]-1,3-thiazol-2-yl}piperidiniumchloride (800 mg).

4-{4-[(1E)-3-(2,6-Difluorophenyl)-3-oxoprop-1-en-1-yl]-1,3-thiazol-2-yl}piperidiniumchloride (300 mg) was reacted analogously to I-24 (step 4) with[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetic acid (183 mg). This gave(2E)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1-(2,6-difluorophenyl)prop-2-en-1-one(100 mg).

log P (pH 2.7): 3.35

¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.51-1.63 (m, 1H), 1.75-1.88 (m,1H), 2.05-2.16 (m, 2.80-2.88 (m, 1H), 3.20-3.42 (m, 2H), 3.92-4.01 (m,1H), 4.30-4.46 (m, 1H), 5.35 (d, 1H), 5.44 (d. 1H), 6.88 (s, 1H), 7.04(t, 1H), 7.15-7.20 (m, 1H), 7.18 (t, 1H), 7.24-7.32 (m, 2H), 7.49 (d,1H), 7.60-7.70 (m, 1H), 8.17 (s, 1H)

MS (ESI): 543 ([M−H]⁺)

The compounds of the formula (I) listed in Table 1 below can be obtainedanalogously to the methods given above:

For all examples of Table 1,

where the bond identified by “v” is attached directly to the piperidinering and where the bond identified by “w” is attached directly to T. Thebond of T identified by “*” is attached to G¹, the bond identified by“#” is attached to R¹.

TABLE I Ex. A L¹ Y T R¹ log P I-1 5-methyl-3-(trifluoromethyl)- CH₂ O*—C═C—CO-# phenyl 3.58^([a]) 1H-pyrazol-1-yl I-25-methyl-3-(trifluoromethyl)- CH₂ O *—C═C—CO-# 2-methoxyphenyl3.35^([a]); 1H-pyrazol-1-yl 3.36^([b]) I-3 5-methyl-3-(trifluoromethyl)-CH₂ O *—C═C—CO-# naphthalen-1-yl 4.25^([a]) 1H-pyrazol-1-yl I-45-methyl-3-(trifluoromethyl)- CH₂ O *—C═C—CO-# cyclohexyl 4.15^([a])1H-pyrazol-1-yl I-5 5-methyl-3-(trifluoromethyl)- CH₂ O *—C═C—CO-#2-chlorophenyl 3.79^([a]) 1H-pyrazol-1-yl I-65-methyl-3-(trifluoromethyl)- CH₂ O *—C═C—CO-# 2,4-dichlorophenyl4.31^([a]) 1H-pyrazol-1-yl I-7 5-methyl-3-(trifluoromethyl)- CH₂ O*—C═C—CO-# 4-methoxyphenyl 3.54^([a]) 1H-pyrazol-1-yl I-85-methyl-3-(trifluoromethyl)- CH₂ O *—C═C—CO-# tert-butyl 3.68^([a])1H-pyrazol-1-yl I-9 5-methyl-3-(trifluoromethyl)- CH₂ O *—C═C—CO-#thiophen-2-yl 3.29^([a]) 1H-pyrazol-1-yl I-105-methyl-3-(trifluoromethyl)- CH₂ O *—C═C—CO-# furan-2-yl 2.92^([a])1H-pyrazol-1-yl I-11 5-methyl-3-(trifluoromethyl)- CH₂ O *—C═C—CO-#2-ethoxyphenyl 3.76^([a]) 1H-pyrazol-1-yl I-125-methyl-3-(trifluoromethyl)- CH₂ O *—CO—CH═CH-[E]-# 2,6-difluorophenyl3.83^([a]) 1H-pyrazol-1-yl I-13 5-methyl-3-(trifluoromethyl)- CH₂ O*—CO—CH₂-# 2-bromophenyl 3.67^([a]); 1H-pyrazol-1-yl 3.71^([b]) I-145-methyl-3-(trifluoromethyl)- CH₂ O *—COCH₂CH₂-# phenyl 3.64^([a])1H-pyrazol-1-yl I-15 5-methyl-3-(trifluoromethyl)- CH₂ O*—CO—CH₂—C(CH₃)₂-# phenyl 4.08^([a]) 1H-pyrazol-1-yl I-165-methyl-3-(trifluoromethyl)- CH₂ O *—CO—CH₂-# phenyl 3.36^([a])1H-pyrazol-1-yl I-17 5-methyl-3-(trifluoromethyl)- CH₂ O *—CO—CH₂-#cyclohexyl 4.13^([a]); 1H-pyrazol-1-yl 4.24^([b]) I-185-methyl-3-(trifluoromethyl)- CH₂ O *—CO—CH₂-# naphthalen-1-yl3.87^([a]) 1H-pyrazol-1-yl I-19 5-methyl-3-(trifluoromethyl)- CH₂ O*—CH₂CH₂—CO-# 2-methoxyphenyl 3.34^([a]) 1H-pyrazol-1-yl I-205-methyl-3-(trifluoromethyl)- CH₂ O *—CH₂CH₂—CO-# 2-ethoxyphenyl3.7^([a]); 1H-pyrazol-1-yl 3.68^([b]) I-21 5-methyl-3-(trifluoromethyl)-CH₂ O *—CH₂CH₂—CO-# 2-chlorophenyl 3.6^([a]); 1H-pyrazol-1-yl 3.63^([b])I-22 3,5-bis(difluoromethyl)- CH₂ O *—CH═CH—CO-[E]-# 2,6-difluorophenyl3.35^([a]) 1H-pyrazol-1-yl I-23 2,5-dimethylphenyl NH O *—CH═CH—CO-[E]-#2,6-difluorophenyl 3.56^([a]) I-24 3,5-bis(difluoromethyl)- CH₂ O*—CO—CH₂-# cyclohexyl 4.02^([a]); 1H-pyrazol-1-yl 4.09^([b]) I-255-chloro-2-methylphenyl NH O *—CO—CH₂-# cyclohexyl 4.51^([a]);4.55^([b]) I-26 5-methyl-3-(trifluoromethyl)- CH₂ O *—C(Cl)═CHCO-[Eand/or phenyl 4^([a]) 1H-pyrazol-1-yl Z]-# I-29 3,5-bis(difluoromethyl)-CH₂ O *—CH═CHCO-[E]-# 2-bromophenyl 3.51^([a]); 1H-pyrazol-1-yl3.49^([b]) I-30 2,5-bis(difluoromethyl)- —NH— O *—COCH₂-# cyclohexyl4.3^([a]); phenyl 4.34^([b]) I-33 3,5-bis(difluoromethyl)- CH₂ O*—CH═CHCO-[E]-# 2-iodophenyl 3.65^([a]); 1H-pyrazol-1-yl 3.64^([b]) I-343,5-Bis(difluoromethyl)- CH₂ O *—CH═CHCO-[E]-# 2-bromo-4-fluorphenyl3.7^([a]); 1H-pyrazol-1-yl 3.68^([b]) I-35 3,5-bis(difluoromethyl)- CH₂O *—CH═CHCO-[E]-# 2-chloro-5-fluorophenyl 3.64^([a]); 1H-pyrazol-1-yl3.6^([b]) I-36 3,5-bis(difluoromethyl)- CH₂ O *—CH═CHCO-[E]-#2-chloro-6-fluorophenyl 3.54^([a]); 1H-pyrazol-1-yl 3.51^([b]) I-373,5-bis(difluoromethyl)- CH₂ O *—CH═CHCO-[E]-# phenyl 3.31^([a]);1H-pyrazol-1-yl 3.31^([b]) I-38 3,5-bis(difluoromethyl)- CH₂ O*—CH═CHCO-[E]-# 3-methylphenyl 3.64^([a]); 1H-pyrazol-1-yl 3.63^([b])I-39 3,5-bis(difluoromethyl)- CH₂ O *—CH═CHCO-[E]-# 2,6-dimethoxyphenyl3.04^([a]) 1H-pyrazol-1-yl I-40 3,5-bis(difluoromethyl)- CH₂ O*—CH═CHCO-[E]-# 4-fluorophenyl 3.43^([a]) 1H-pyrazol-1-yl I-413,5-bis(difluoromethyl)- CH₂ O *—CH═CHCO-[E]-# 3-fluorophenyl 3.48^([a])1H-pyrazol-1-yl I-42 3,5-bis(difluoromethyl)- CH₂ O *—CH═CHCO-[E]-#2-chlorophenyl 3.51^([a]) 1H-pyrazol-1-yl I-43 3,5-bis(difluoromethyl)-CH₂ O *—CH═CHCO-[E]-# 2,6-dichlorophenyl 3.7^([a]) 1H-pyrazol-1-yl I-443,5-bis(difluoromethyl)- CH₂ O *—CH═CHCO-[E]-# cyclohexyl 3.89^([a])1H-pyrazol-1-yl I-45 3,5-bis(difluoromethyl)- CH₂ O *—CH═CHCO-[E]-#2-methylphenyl 3.56^([a]) 1H-pyrazol-1-yl I-46 3,5-bis(difluoromethyl)-CH₂ O *—CH═CHCO-[E]-# naphthalen-1-yl 2.84^([a]) 1H-pyrazol-1-yl I-473,5-bis(difluoromethyl)- CH₂ O *—CH═CHCO-[E]-# tert-butyl 3.45^([a])1H-pyrazol-1-yl I-48 3,5-bis(difluoromethyl)- CH₂ O *—CH═CHCO-[E]-#2-fluoro-4-methoxyphenyl 3.45^([a]) 1H-pyrazol-1-yl I-493,5-bis(difluoromethyl)- CH₂ O *—CH═CHCO-[E]-# cyclopentyl 3.52^([a])1H-pyrazol-1-yl I-50 3,5-bis(difluoromethyl)- CH₂ O *—CH═CHCO-[E]-#2-methylcyclohexyl 4.11^([a]) 1H-pyrazol-1-yl I-513,5-bis(difluoromethyl)- CH₂ O *—CH(CH3)CH₂CO-# 2,6-difluorophenyl1H-pyrazol-1-yl I-52 3,5-bis(difluoromethyl)- CH₂ O *—CH═CHCO-[E]-#3-fluorophenyl 3.35^([a]) 1H-pyrazol-1-yl I-55 3,5-bis(difluoromethyl)-CH₂ O *—CH═CHCO-[E]-# 2-(prop-2-yn-1-yloxy)phenyl 3.28^([a])1H-pyrazol-1-yl I-57 3,5-bis(difluoromethyl)- CH₂ O *—CH═CHCO-[E]-#2,4,6-trifluorophenyl 3.51^([a]); 1H-pyrazol-1-yl 3.5^([b]) I-583,5-bis(difluoromethyl)- CH₂ S *—COCH₂-# cyclohexyl 4.63^([a]);1H-pyrazol-1-yl 4.56^([b]) I-59 3,5-bis(difluoromethyl)- CH₂ O *—COCH₂-#2,3-dimethylphenyl 3.71^([a]) 1H-pyrazol-1-yl I-603,5-bis(difluoromethyl)- CH₂ O *—C(═NOCH₃)CH₂-[Z]-# cyclohexyl 4.8^([a])1H-pyrazol-1-yl I-61 3,5-bis(difluoromethyl)- CH₂ O *—C(═NOCH₃)CH₂-[Z]-#2,3-dimethylphenyl 4.33^([a]) 1H-pyrazol-1-yl I-623,5-bis(difluoromethyl)- CH₂ O *—COCH═CH-[E]-# 2,6-difluorophenyl3.68^([a]); 1H-pyrazol-1-yl 3.59^([b]) I-63 3,5-bis(difluoromethyl)- CH₂O *—CH═CHCO-[E]-# 2,6-dimethylphenyl 3.65^([a]); 1H-pyrazol-1-yl3.64^([b]) I-64 3,5-bis(difluoromethyl)- CH₂ O *—CH═CHC(═NOH)-[E,E]-#2-(prop-2-yn-1-yloxy)phenyl 3.08^([a][d]); 1H-pyrazol-1-yl 3.30^([a][e])I-65 5-methyl-3-(trifluoromethyl)- CH₂ O *—C(Cl)═CHCO-[E and/or2-methoxyphenyl 3.96^([a][d]); 1H-pyrazol-1-yl Z]-# 3.79^([a][e])^([d])major isomer; ^([e])minor isomer The logP values were determinedaccording to EEC directive 79/831 Annex V.A8 by HPLC (High PerformanceLiquid Chromatography) on reversed-phase columns (C 18), using themethods below: ^([a])The LC-MS determination in the acidic range iscarried out at pH 2.7 using the mobile phases 0.1% aqueous formic acidand acetonitrile (contains 0.1% formic acid); linear gradient from 10%acetonitrile to 95% acetonitrile ^([b])The LC-MS determination in theneutral range is carried out at pH 7.8 using the mobile phases 0.001molar aqueous ammonium bicarbonate solution and acetonitrile; lineargradient from 10% acetonitrile to 95% acetonitrile

Calibration was carried out using unbranched alkan-2-ones (having from 3to 16 carbon atoms) with known log P values (the log P values weredetermined by the retention times using linear interpolation between twosuccessive alkanones).

The lambda max values were determined in the maxima of thechromatographic signals using the UV spectra from 200 nm to 400 nm.

NMR Data of Selected Examples

Ex. NMR data I-1 ¹H NMR (CD₃CN, 400 MHz): δ_(ppm): 1.65-1.76 (m, 1H),1.83-1.95 (m, 1H), 2.10-2.21 (m, 2H), 2.23 (s, 3H), 2.82-2.91 (m, 1H),3.25-3.40 (m, 2H), 3.90-3.98 (m, 1H), 4.45-4.53 (m, 1H), 5.04 (d, 1H),5.11 (d, 1H), 6.40 (s, 1H), 7.56-7.63 (m, 2H), 7.70-7.75 (m, 1H), 8.08(s, 1H), 8.18-8.22 (m, 2H) I-2 ¹H NMR (CD₃CN, 400 MHz): δ_(ppm):1.65-1.76 (m, 1H), 1.83-1.95 (m, 1H), 2.10-2.20 (m, 2H), 2.23 (s, 3H),2.82-2.91 (m, 1H), 3.25-3.39 (m, 2H), 3.90-3.97 (m, 1H), 3.95 (s, 3H),4.45-4.51 (m, 1H), 5.04 (d, 1H), 5.11 (d, 1H), 6.39 (s, 1H), 7.08 (t,1H), 7.17 (d, 1H), 7.60-7.65 (m, 1H), 7.97 (s, 1H), 7.97-8.00 (m, 1H)I-3 ¹H NMR (CD₃CN, 400 MHz): δ_(ppm): 1.65-1.78 (m, 1H), 1.82-1.95 (m,1H), 2.13-2.20 (m, 2H), 2.23 (s, 3H), 2.80-2.90 (m, 1H), 3.25-3.40 (m,2H), 3.90-3.98 (m, 1H), 4.45-4.53 (m, 1H), 5.04 (d, 1H), 5.11 (d, 1H),6.40 (s, 1H), 7.10-7.25 (m, 3H), 8.02 (d, 1H), 8.06 (s, 1H), 8.23 (d,1H), 8.69 (d, 1H), 9.15 (d, 1H) I-4 ¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm):1.15-1.48 (m, 5H), 1.50-1.88 (m, 5H), 1.92-1.99 (m, 2H), 2.07-2.15 (m,2H), 2.22 (s, 3H), 2.50-2.59 (m, 1H), 2.88 (bs, 1H), 3.20-3.41 (m, 2H),3.99 (bs, 1H), 4.32 (bs, 1H), 5.21 (bs, 2H), 6.45 (s, 1H), 8.31 (a, 1H)I-5 ¹H NMR (CD₃CN, 400 MHz): δ_(ppm): 1.70-1.95 (m, 2H), 2.18-2.25 (m,2H), 2.29 (s, 3H), 2.97 (bs, 1H), 3.25-3.44 (m, 2H), 4.01 (bs, 1H), 4.50(bs, 1H), 5.10 (bs, 2H), 6.42 (s, 1H), 7.52-7.65 (m, 3H), 8.05 (s, 1H),8.16 (dd, 1H) I-6 ¹H NMR (CD₃CN, 400 MHz): δ_(ppm): 1.64-1.74 (m, 1H),1.80-1.91 (m, 1H), 2.10-2.23 (m, 2H), 2.23 (s, 3H), 2.80-2.89 (m, 1H),3.25-3.38 (m, 2H), 3.89-3.95 (m, 1H), 4.45-4.51 (m, 1H), 5.04 (d, 1H),5.11 (d, 1H), 6.39 (s, 1H), 7.53 (dd, 1H), 7.63 (d, 1H), 8.06 (s, 1H),8.14 (d, 1H) I-7 ¹H NMR (CD₃CN, 400 MHz): δ_(ppm): 1.71-2.05 (m, 2H),2.11-2.21 (m, 2H), 2.24 (s, 3H), 2.90 (bs, 1H), 3.24-3.40 (m, 2H), 3.90(s, 3H), 3.98 (bs, 1H), 4.45 (bs, 1H), 5.05 (bs, 2H), 6.37 (s, 1H),7.05-7.95 (m, 2H), 7.99 (s, 1H), 8.13-8.18 (m, 2H) I-8 ¹H NMR (CD₃CN,400 MHz): δ_(ppm): 1.25 (s, 9H), 1.62-1.90 (m, 2H), 2.10-2.19 (m, 2H),2.24 (s, 3H), 2.89 (bs, 1H), 3.20-3.37 (m, 2H), 3.95 (bs, 1H), 4.44 (bs,1H), 5.04 (bs, 2H), 6.36 (s, 1H), 7.89 (s, 1H) I-9 ¹H NMR (CD₃CN, 400MHz): δ_(ppm): 1.70-1.95 (m, 2H), 2.13-2.22 (m, 2H), 2.24 (s, 3H), 2.91(bs, 1H), 3.23-3.40 (m, 2H), 3.95 (bs, 1H), 4.44 (bs, 1H), 5.05 (bs,2H), 6.37 (s, 1H), 7-26 (dd, 1H), 7.90 (dd, 1H), 8.01 (s, 1H), 8.06 (dd,1H) I-10 ¹H NMR (CD₃CN, 400 MHz): δ_(ppm): 1.68-1.95 (m, 2H), 2.10-2.20(m, 2H), 2.24 (s, 3H), 2.92 (bs, 1H), 3.22-3.40 (m, 2H), 3.98 (bs, 1H),4.46 (bs, 1H), 5.05 (bs, 2H), 6.37 (s, 1H), 6.69 (dd, 1H), 7.52 (d, 1H),7.82 (d, 1H), 7.99 (s, 1H) I-11 ¹H NMR (CD₃CN, 400 MHz): δ_(ppm): 1.44(t, 3H), 1.65-1.95 (m, 2H), 2.12-2.21 (m, 2H), 2.24 (s, 3H), 2.90 (bs,1H), 3.25-3.38 (m, 2H), 3.95 (bs, 1H), 4.22 (q, 2H), 4.43 (1H), 5.04(bs, 2H), 6.37 (s, 1H), 7.02-7.18 (m, 2H), 7.54-7.60 (m, 1H), 7.87 (dd,1H), 7.89 (s, 1H) I-12 ¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.56-1.68 (m,1H), 1.78-1.91 (m, 1H), 2.10-2.21 (m, 2H), 2.22 (s, 3H), 2.84-2.92 (m,1H), 3.20-3.50 (m, 2H), 3.95-4.05 (m, 1H), 4.36-4.92 (m, 1H), 5.23 (d,1H), 5.34 (d, 1H), 6.50 (s, 1H), 7.26 (d, 1H), 7.28 (d, 1H), 7.58 (m,1H), 7.81 (d, 1H), 8.07 (d, 1H), 8.626 (s, 1H) I-13 ¹H NMR (DMSO-d₆, 400MHz): δ_(ppm): 1.56-1.68 (m, 1H), 1.80-1.91 (m, 1H), 2.10-2.22 (m, 2H),2.22 (s, 3H), 2.83-2.92 (m, 1H), 3.25-3.35 (m, 1H), 3.40-3.48 (m, 1H),3.96-4.03 (m, 1H), 4.35-4.42 (m, 1H), 4.57 (s, 2H), 5.24 (d, 1H), 5.33(d, 1H), 6.50 (s, 1H), 7.23 (td, 1H), 7.33-7.42 (m, 2H), 7.62 (dd, 1H),8.54 (s, 1H) I-14 ¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.41 (s, 9H),1.48-1.61 (m, 2H), 1.90-2.11 (4H), 2.62-2.67 (m, 2H), 2.87-2.95 (m, 2H),3.15-3.20 (m, 1H), 3.94-4.00 (2H), 4.62-4.67 (m, 1H), 5.09-5.12 (m, 1H),7.11-7.18 (m, 3H), 7.22-7.27 (m, 3H) I-15 ¹H NMR (DMSO-d₆, 400 MHz):δ_(ppm): 1.41 (s, 6H), 1.52-1.85 (m, 2H), 2.08-2.15 (m, 2H), 2.23 (s,3H), 2.90 (bs, 1H), 3.20-3.40 (m, 2H), 3.41 (s, 2H), 3.99 (bs, 1H), 4.34(bs, 1H), 5.22 (bs, 2H), 6.45 (s, 1H), 7.08-7.13 (m, 1H), 7.21-7.26 (m,2H), 7.35-7.39 (m, 2H), 8.22 (s, 1H) I-16 ¹H NMR (DMSO-d₆, 400 MHz):δ_(ppm): 1.58-1.90 (m, 2H), 2.12-2.19 (m, 2H), 2.23 (s, 3H), 2.93 (bs,1H), 3.31 (bs, 1H), 3.36-3.47 (m, 1H), 4.00 (bs, 1H), 4.32 (bs, 1H),4.33 (s, 2H), 5.17-5.27 (m, 2H), 6.45 (s, 1H), 7.18-7.32 (m, 5H), 8.43(s, 1H) I-17 ¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 0.94-1.05 (m, 2H),1.10-1.29 (m, 3H), 1.54-1.71 (m, 6H), 1.75-1.93 (m, 2H), 2.06-2.18 (m,2H), 2.21 (s, 3H), 2.81-2.89 (m, 1H), 2.89 (d, 2H), 3.22-3.45 (m, 2H),3.94-4.01 (m, 1H), 4.33-4.40 (m, 1H), 5.22 (d, 1H), 5.33 (d, 1H), 6.50(s, 1H), 8.42 (s, 1H) I-18 ¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.60-1.91(m, 2H), 2.11-2.21 (m, 2H), 2.23 (s, 3H), 2.92 (bs, 1H), 3.31 (bs, 1H),3.40-3.49 (m, 1H), 4.02 (bs, 1H), 4.34 (bs, 1H), 4.83 (s, 2H), 5.22 (bs,2H), 6.45 (s, 1H), 7.43-7.52 (m, 3H), 7.79-7.82 (m, 2H), 7.88-7.94 (m,1H), 7.97-8.01 (m, 1H), 8.46 (s, 1H) I-19 ¹H NMR (CD₃CN, 400 MHz):δ_(ppm): 1.55-1.67 (m, 1H), 1.72-1.83 (m, 1H), 2.03-2.14 (m, 2H), 2.22(s, 3H), 2.79-2.87 (m, 1H), 3.06 (t, 2H), 3.19-3.35 (m, 2H), 3.34 (t,2H), 3.85-3.92 (m, 1H), 3.88 (s, 3H), 4.40-4.46 (m, 1H), 5.03 (d, 1H),5.08 (d, 1H), 6.39 (s, 1H), 6.98 (s, 1H), 7.00 (t, 1H), 7.09 (d, 1H),7.45-7.56 (m, 2H) I-20 ¹H NMR (CD₃CN, 400 MHz): δ_(ppm): 1.44 (t, 3H),1.58-1.70 (m, 1H), 1.75-1.86 (m, 1H), 2.06-2.18 (m, 2H), 2.25 (s, 3H),2.82-2.90 (m, 1H), 3.09 (t, 2H), 3.20-3.32 (m, 2H), 3.42 (t, 2H),3.88-3.95 (m, 1H), 4.16 (q, 2H), 4.42-4.47 (m, 1H), 5.04 (d, 1H), 5.11(d, 1H), 6.42 (s, 1H), 6.95 (s, 1H), 7.01 (t, 1H), 7.09 (d, 1H),7.47-7.53 (m, 1H), 5.59 (dd, 1H) I-21 ¹H NMR (CD₃CN, 400 MHz): δ_(ppm):1.55-1.66 (m, 1H), 1.71-1.82 (m, 1H), 2.02-2.15 (m, 2H), 2.22 (s, 3H),2.78-2.86 (m, 1H), 3.08 (t, 2H), 3.18-3.33 (m, 2H), 3.32 (t, 2H),3.85-3.92 (m, 1H). 4.39-4.46 (m, 1H), 5.02 (d, 1H), 5.09 (d, 1H), 6.39(s, 1H), 6.96 (s, 1H), 7.35-7.52 (m, 4H) I-22 ¹H NMR (DMSO-d₆, 400 MHz):δ_(ppm): 1.51-1.63 (m, 1H), 1.75-1.88 (m, 1H), 2.05-2.16 (m, 2H),2.80-2.88 (m, 1H), 3.20-3.42 (m, 2H), 3.92-4.01 (m, 1H), 4.30-4.46 (m,1H), 5.35 (d, 1H), 5.44 (d. 1H), 6.88 (s, 1H), 7.04 (t, 1H), 7.15-7.20(m, 1H), 7.18 (t, 1H), 7.24-7.32 (m, 2H), 7.49 (d, 1H), 7.60-7.70 (m,1H), 8.17 (s, 1H) I-23 ¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 1.62-1.69 (m,2H), 2.05-2.09 (m, 2H), 2.11 (s, 3H), 2.23 (s, 3H), 2.95-3.01 (m, 2H),3.29-3.35 (m, 1H), 4.13-4.17 (m, 2H), 6.86 (d, 1H), 6.99 (s, 1H), 7.04(d, 1H), 7.17 (d, 1H), 7.27-7.32 (m, 2H), 7.49 (d, 1H), 7.63-7.68 (m,1H), 8.03 (s, 1H), 8.18 (s, 1H) I-24 ¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm):0.95-1.02 (m, 2H), 1.10-1.26 (m, 3H), 1.54-1.69 (m, 6H), 1.77-1.91 (m,2H), 2.06-2.15 (m, 2H), 2.82-2.87 (m, 1H), 2.89 (d, 2H), 3.25-3.30 (m,1H), 3.35-3.41 (m, 1H), 3.94-3.99 (m, 1H), 4.33-4.37 (m, 1H), 5.36 (d,1H), 5.45 (d, 1H), 6.91 (s, 1H), 7.04 (t, 1H), 7.18 (t, 1H), 8.44 (s,1H) I-25 ¹H NMR (DMSO-d₆, 400 MHz): δ_(ppm): 0.94-1.05 (m, 2H),1.10-1.26 (m, 4H), 1.56-1.73 (m, 6H), 1.83-1.92 (m, 1H), 2.06-2.13 (m,2H), 2.16 (s, 3H), 2.88 (d, 2H), 2.98-2.06 (m, 2H), 3.30-3.38 (m, 1H),4.11-4.18 (m, 2H), 7.07 (dd, 1H), 7.19 (d, 1H), 7.33 (d, 1H), 8.12 (s,1H), 8.04 (s, 1H)

The 1H-NMR data of selected examples are given in the form of 1H-NMRpeak lists. For each signal peak, the δ value in ppm and the signalintensity are listed:

Ex. NMR peak list data I-26 [DMSO-D₆] 8.1231 6.35; 8.0482 7.38; 7.97510.56; 7.9599 2.84; 7.9569 3.62; 7.9443 1.14; 7.9392 4.50; 7.9357 3.58;7.8555 0.74; 7.8509 1.42; 7.8379 0.77; 7.8343 0.72; 7.6973 0.46; 7.69390.91; 7.6907 0.51; 7.6806 0.67; 7.6755 2.23; 7.6706 0.80; 7.6604 1.05;7.6571 1.85; 7.6537 0.93; 7.5924 3.06; 7.5886 1.33; 7.5760 2.41; 7.57294.24; 7.5589 1.05; 7.5547 2.02; 7.5528 1.33; 7.5417 0.38; 7.4696 0.59;7.4502 0.78; 7.4321 0.37; 7.0164 1.35; 6.4681 0.77; 6.4582 0.72; 6.44853.44; 5.6885 5.31; 5.2322 0.85; 5.2161 0.86; 5.1375 1.62; 4.9763 2.78;4.0644 0.46; 4.0468 1.31; 4.0289 1.42; 4.0112 0.61; 3.5676 0.65; 3.44370.34; 3.4342 0.61; 3.4244 0.38; 3.4159 0.68; 3.4063 1.22; 3.3965 0.76;3.3876 0.47; 3.3782 0.74; 3.3689 0.42; 3.2752 0.36; 3.2544 0.34; 3.1201134.75; 3.0183 0.50; 2.9006 0.33; 2.6626 0.42; 2.6579 0.59; 2.6533 0.42;2.5272 0.49; 2.5111 1.30; 2.5064 1.84; 2.4982 32.10; 2.4935 66.61;2.4888 94.30; 2.4841 66.08; 2.4794 31.81; 2.3203 0.38; 2.3157 0.60;2.3109 0.44; 2.2578 3.63; 2.2563 3.71; 2.2265 15.73; 2.2250 16.00;2.1931 0.80; 2.1744 0.92; 2.1442 1.08; 2.0406 0.95; 1.9742 5.50; 1.90150.40; 1.6943 0.40; 1.6725 0.38; 1.6649 0.36; 1.6591 0.40; 1.6396 0.35;1.2449 0.45; 1.1952 1.59; 1.1774 3.19; 1.1597 1.59; −0.0001 2.84 I-29[DMSO-D₆] 8.1441 11.91; 7.7596 3.68; 7.7418 3.77; 7.7397 4.01; 7.68020.35; 7.6610 0.38; 7.5576 1.03; 7.5549 1.06; 7.5382 3.23; 7.5215 4.67;7.5188 4.35; 7.5112 3.71; 7.5060 6.34; 7.4917 5.35; 7.4861 3.10; 7.47452.90; 7.4721 3.56; 7.4689 2.31; 7.4665 2.27; 7.4549 1.87; 7.4492 1.33;7.4147 0.37; 7.4013 0.34; 7.3191 4.88; 7.3060 2.61; 7.2797 8.40; 7.19720.86; 7.1779 8.71; 7.1727 6.14; 7.1580 2.85; 7.1386 4.51; 7.0394 2.75;7.0219 6.38; 6.8997 5.57; 6.8860 3.13; 5.4484 1.02; 5.4057 4.32; 5.36964.24; 5.3445 0.38; 5.3267 1.03; 4.3555 1.27; 4.3222 1.34; 4.0571 1.33;4.0393 3.75; 4.0215 3.79; 4.0038 1.44; 3.9800 1.26; 3.9453 1.36; 3.47810.43; 3.4577 0.49; 3.4356 0.72; 3.4109 1.52; 3.4017 1.30; 3.3918 1.86;3.3825 2.70; 3.3729 2.13; 3.3631 2.09; 3.3537 2.84; 3.3057 573.68;3.2826 9.11; 3.2429 1.20; 2.8901 1.16; 2.8789 0.91; 2.8508 1.60; 2.82060.91; 2.7321 0.68; 2.6740 0.89; 2.6695 1.12; 2.6648 0.82; 2.5394 2.52;2.5091 62.88; 2.5048 112.86; 2.5004 143.95; 2.4960 99.46; 2.4917 47.75;2.3315 0.71; 2.3271 0.91; 2.3225 0.67; 2.1468 1.23; 2.1107 2.33; 2.06971.63; 1.9869 16.00; 1.8609 0.43; 1.8514 0.48; 1.8237 1.11; 1.8017 0.98;1.7928 0.89; 1.7702 0.38; 1.6262 0.43; 1.6163 0.48; 1.5961 1.00; 1.58791.06; 1.5650 0.98; 1.5573 0.90; 1.5367 0.40; 1.2363 0.48; 1.1928 4.35;1.1750 8.73; 1.1572 4.22; 0.9264 0.37; 0.0080 0.67; −0.0002 11.85;−0.0084 0.46 I-30 [DMSO-D₆] 8.6206 4.81; 8.4136 16.00; 7.7324 0.47;7.7047 2.72; 7.6850 3.18; 7.5317 4.01; 7.4853 2.48; 7.4658 2.02; 7.22012.26; 7.2139 1.78; 7.0810 4.92; 7.0761 4.14; 6.9500 0.37; 6.9418 2.61;4.2512 0.33; 4.2282 0.34; 4.1744 2.50; 4.1403 2.58; 4.0571 0.57; 4.03931.54; 4.0215 1.61; 4.0036 0.60; 3.7222 1.42; 3.7090 0.46; 3.6975 0.44;3.5947 0.39; 3.5678 1.69; 3.4175 0.41; 3.4044 0.54; 3.3904 1.05; 3.38101.53; 3.3707 1.63; 3.3619 2.31; 3.3517 3.59; 3.3135 2176.06; 3.290033.84; 3.2738 1.64; 3.2531 0.61; 3.0807 1.68; 3.0522 3.15; 3.0228 1.72;2.8922 9.42; 2.8752 9.74; 2.6790 0.68; 2.6744 1.35; 2.6699 1.88; 2.66511.34; 2.6608 0.69; 2.5398 3.16; 2.5231 5.65; 2.5184 8.38; 2.5097 103.40;2.5053 202.26; 2.5008 272.55; 2.4963 187.40; 2.4918 88.41; 2.3320 1.34;2.3275 1.94; 2.3229 1.39; 2.3182 0.64; 2.1176 2.00; 2.0914 2.31; 2.08562.24; 2.0691 6.17; 2.0494 0.37; 1.9869 6.91; 1.9197 0.44; 1.9097 0.65;1.9003 0.94; 1.8916 0.94; 1.8828 1.19; 1.8743 1.04; 1.8649 0.76; 1.85550.77; 1.8460 0.49; 1.8393 0.33; 1.7467 0.73; 1.7363 0.91; 1.7146 1.85;1.7063 2.08; 1.6841 4.03; 1.6751 4.16; 1.6565 4.64; 1.6501 3.99; 1.63252.59; 1.6263 2.30; 1.5853 1.04; 1.3985 0.45; 1.2841 0.36; 1.2718 0.58;1.2411 1.68; 1.2180 1.77; 1.2099 2.18; 1.1928 2.46; 1.1874 1.53; 1.17515.58; 1.1572 2.51; 1.1491 1.32; 1.1195 0.86; 1.0386 0.94; 1.0324 1.09;1.0041 2.29; 0.9743 1.82; 0.9499 0.64; 0.9395 0.49; −0.0001 5.55 I-33[DMSO-D₆] 8.1416 7.23; 7.9858 2.56; 7.9664 2.64; 7.5640 1.19; 7.54622.69; 7.5281 1.81; 7.4712 0.37; 7.4521 2.56; 7.4481 2.76; 7.4331 2.10;7.4292 1.92; 7.4220 0.39; 7.3303 0.72; 7.3051 1.95; 7.2949 4.15; 7.27932.46; 7.2753 2.39; 7.2557 6.06; 7.2010 0.33; 7.1713 4.28; 7.1679 5.64;7.1572 1.93; 7.1284 2.66; 7.0388 1.80; 7.0211 3.80; 6.9590 0.32; 6.90003.83; 6.8854 1.90; 5.4476 0.81; 5.4045 2.98; 5.3871 0.76; 5.3690 2.96;5.3273 0.85; 4.3570 1.12; 4.3185 1.12; 4.2594 0.41; 4.2556 0.36; 4.17210.48; 4.1607 0.41; 4.1086 0.44; 4.0905 0.48; 4.0727 0.51; 4.0568 1.63;4.0392 4.13; 4.0215 4.29; 4.0034 1.80; 3.9821 1.27; 3.9679 1.10; 3.94561.34; 3.9094 0.67; 3.8857 0.67; 3.8808 0.78; 3.8652 0.75; 3.8537 0.73;3.7222 1.37; 3.6832 1.62; 3.6610 1.85; 3.6523 1.86; 3.6335 2.02; 3.62981.99; 3.5555 2.99; 3.4880 4.86; 3.3256 3385.14; 3.2484 4.44; 3.19742.05; 3.1152 1.41; 3.1033 1.39; 3.0967 1.29; 3.0836 1.22; 3.0670 1.02;3.0343 1.05; 3.0223 0.96; 2.9873 0.87; 2.9446 0.88; 2.9150 0.86; 2.90140.97; 2.8821 1.42; 2.8499 2.05; 2.8220 1.49; 2.7990 1.00; 2.7843 1.05;2.7708 1.02; 2.7565 1.08; 2.7296 1.25; 2.6955 2.61; 2.6702 3.41; 2.66612.97; 2.5403 11.32; 2.5057 258.17; 2.5014 323.27; 2.4973 233.05; 2.43291.69; 2.4245 1.31; 2.4158 1.07; 2.3762 0.73; 2.3676 0.70; 2.3320 2.03;2.3281 2.50; 2.2801 0.54; 2.2681 0.50; 2.2450 0.46; 2.2164 0.51; 2.19670.60; 2.1900 0.52; 2.1779 0.78; 2.1570 1.27; 2.1516 1.30; 2.1150 2.00;2.0844 1.70; 2.0686 2.66; 2.0489 0.68; 2.0398 0.47; 2.0179 0.55; 1.986716.00; 1.9595 0.42; 1.9414 0.36; 1.9203 0.46; 1.9076 0.60; 1.9035 0.58;1.8815 0.49; 1.8643 0.62; 1.8534 0.78; 1.8276 1.06; 1.8055 0.93; 1.77440.56; 1.7633 0.52; 1.7524 0.36; 1.7370 0.40; 1.7172 0.32; 1.6846 0.33;1.6321 0.58; 1.6218 0.57; 1.5907 1.01; 1.5674 0.96; 1.5634 0.92; 1.43470.33; 1.3982 1.38; 1.2917 0.36; 1.2355 0.75; 1.2291 0.51; 1.2133 0.47;1.1929 4.61; 1.1751 8.54; 1.1574 4.31; 1.0366 0.33; −0.0002 5.53 I-34[DMSO-D₆] 8.1326 4.77; 7.7556 1.35; 7.7495 1.36; 7.7338 1.36; 7.72771.30; 7.6227 1.19; 7.6075 1.32; 7.6013 1.54; 7.5861 1.39; 7.4392 0.85;7.4330 0.81; 7.4179 1.53; 7.4117 1.40; 7.3966 0.72; 7.3904 0.66; 7.35182.08; 7.3126 3.32; 7.3064 1.15; 7.1775 3.36; 7.1732 2.50; 7.1580 1.13;7.1384 1.91; 7.0399 1.10; 7.0219 2.47; 6.9006 2.17; 6.8860 1.21; 5.45010.42; 5.4064 1.72; 5.3694 1.67; 5.3271 0.42; 4.3574 0.53; 4.3232 0.53;4.0571 1.27; 4.0392 3.71; 4.0214 3.73; 4.0036 1.33; 3.9819 0.51; 3.94770.55; 3.4127 0.72; 3.4027 0.68; 3.3938 0.92; 3.3840 1.30; 3.3745 1.13;3.3083 410.62; 3.2447 0.51; 2.8802 0.36; 2.8502 0.67; 2.8210 0.37;2.6741 0.43; 2.6694 0.57; 2.6647 0.42; 2.5396 1.36; 2.5093 31.74; 2.504957.40; 2.5005 73.67; 2.4961 51.08; 2.4917 24.52; 2.3320 0.35; 2.32720.46; 2.3227 0.32; 2.1467 0.53; 2.1121 0.92; 2.0693 0.85; 1.9868 16.00;1.8299 0.41; 1.8237 0.46; 1.7994 0.38; 1.7922 0.36; 1.5982 0.41; 1.58940.42; 1.5672 0.38; 1.5578 0.36; 1.1928 4.47; 1.1750 8.78; 1.1572 4.31;−0.0002 2.18 I-35 [DMSO-D₆] 8.1524 10.14; 7.6638 2.28; 7.6518 2.45;7.6417 2.83; 7.6297 2.73; 7.5019 2.25; 7.4944 3.06; 7.4809 2.39; 7.47333.03; 7.4636 2.19; 7.4559 1.54; 7.4427 2.99; 7.4346 2.07; 7.4209 1.82;7.4132 1.23; 7.3880 4.78; 7.3486 6.57; 7.3068 2.09; 7.2890 0.40; 7.21890.39; 7.1709 7.64; 7.1580 2.65; 7.1313 4.26; 7.0462 0.74; 7.0403 2.41;7.0220 5.38; 6.9590 0.34; 6.9009 4.78; 6.8861 2.72; 5.7461 16.00; 5.44940.94; 5.4074 3.67; 5.3893 0.62; 5.3699 3.71; 5.3271 0.90; 5.2962 0.85;4.3562 1.10; 4.3249 1.13; 4.2641 0.33; 4.2522 0.39; 4.2400 0.34; 4.05720.84; 4.0395 2.42; 4.0217 2.47; 4.0039 0.95; 3.9826 1.07; 3.9495 1.17;3.6968 0.35; 3.6930 0.36; 3.6843 0.55; 3.6729 0.75; 3.6637 0.58; 3.65120.38; 3.5681 0.54; 3.4416 0.48; 3.4149 1.26; 3.4056 1.13; 3.3956 1.61;3.3864 2.39; 3.3769 1.98; 3.3671 2.06; 3.3138 679.74; 3.2457 1.26;3.0376 0.32; 2.8818 0.78; 2.8506 1.55; 2.8225 0.79; 2.6748 0.58; 2.67010.76; 2.6656 0.56; 2.5401 1.68; 2.5098 43.12; 2.5055 78.38; 2.5011100.99; 2.4967 70.61; 2.4924 34.59; 2.3325 0.54; 2.3278 0.69; 2.32320.54; 2.1470 1.05; 2.1123 2.00; 2.0694 1.35; 1.9871 10.39; 1.8628 0.39;1.8583 0.40; 1.8521 0.45; 1.8320 0.89; 1.8239 0.98; 1.8014 0.84; 1.77150.36; 1.7633 0.32; 1.6205 0.46; 1.5984 0.89; 1.5901 0.95; 1.5688 0.87;1.5608 0.83; 1.5391 0.36; 1.2359 0.41; 1.1930 2.90; 1.1753 5.73; 1.15742.83; −0.0002 3.83 I-36 [DMSO-D₆] 8.1773 7.83; 7.6322 0.91; 7.6164 1.11;7.6117 2.06; 7.5960 2.17; 7.5909 1.51; 7.5752 1.34; 7.4931 3.38; 7.47292.41; 7.4336 1.63; 7.4113 2.75; 7.3872 3.63; 7.3470 4.08; 7.3062 1.64;7.1729 3.65; 7.1584 1.82; 7.1246 4.22; 7.0852 3.07; 7.0397 1.80; 7.02234.02; 6.9007 3.62; 6.8864 2.01; 5.4484 0.70; 5.4053 2.95; 5.3701 2.86;5.3281 0.70; 4.3546 0.89; 4.3227 0.91; 4.0572 1.28; 4.0395 3.75; 4.02173.79; 4.0039 1.37; 3.9818 0.86; 3.9475 0.93; 3.4377 0.56; 3.4221 0.84;3.4139 1.17; 3.4041 1.11; 3.3951 1.53; 3.3857 2.19; 3.3762 1.98; 3.3136766.08; 3.2443 1.08; 2.8810 0.62; 2.8506 1.18; 2.8241 0.66; 2.6747 0.64;2.6701 0.82; 2.6654 0.62; 2.5399 1.92; 2.5097 49.29; 2.5055 88.69;2.5011 113.23; 2.4967 79.02; 2.4926 38.38; 2.3323 0.57; 2.3278 0.74;2.3229 0.57; 2.1466 0.85; 2.1100 1.57; 2.0693 1.39; 1.9871 16.00; 1.85430.33; 1.8317 0.68; 1.8244 0.76; 1.8027 0.69; 1.6207 0.34; 1.6005 0.67;1.5914 0.71; 1.5697 0.67; 1.5619 0.63; 1.4039 0.53; 1.1930 4.42; 1.17528.75; 1.1574 4.28; −0.0002 2.58 I-37 [DMSO-D₆] 8.1616 16.00; 8.04018.89; 8.0224 10.20; 8.0188 8.00; 7.9030 0.42; 7.8856 0.55; 7.8818 0.43;7.8365 5.64; 7.7983 10.55; 7.7190 11.16; 7.7010 2.08; 7.6979 1.48;7.6813 9.55; 7.6672 2.70; 7.6642 4.06; 7.6611 2.34; 7.6069 7.16; 7.587510.45; 7.5693 4.54; 7.4781 0.36; 7.4590 0.50; 7.3184 3.26; 7.1851 7.42;7.1645 3.65; 7.0519 3.67; 7.0285 8.29; 6.9891 0.40; 6.9572 0.46; 6.90767.49; 6.8926 4.22; 6.6263 0.45; 6.5951 0.37; 5.4668 1.50; 5.4242 5.66;5.3824 5.56; 5.3398 1.53; 5.3181 0.75; 4.3941 1.69; 4.3606 1.77; 4.05711.03; 4.0393 3.16; 4.0215 3.78; 4.0038 2.55; 3.9740 1.79; 3.5680 0.97;3.4493 0.98; 3.4400 1.67; 3.4303 1.35; 3.4209 2.07; 3.4113 3.29; 3.40182.38; 3.3922 2.10; 3.3823 2.85; 3.3729 2.70; 3.3125 1921.95; 3.16720.70; 3.1034 0.49; 3.0697 0.43; 3.0466 0.38; 3.0374 0.40; 2.8905 1.40;2.8613 2.26; 2.8325 1.34; 2.6954 0.60; 2.6790 0.84; 2.6745 1.47; 2.66991.90; 2.6652 1.43; 2.5399 4.06; 2.5229 9.24; 2.5095 110.27; 2.5053201.65; 2.5008 260.70; 2.4965 183.97; 2.4922 90.87; 2.3322 1.53; 2.32761.98; 2.3230 1.51; 2.1793 1.79; 2.1479 3.46; 2.1144 1.92; 2.0693 0.89;1.9869 13.51; 1.9082 0.69; 1.8916 0.66; 1.8836 0.82; 1.8623 1.46; 1.85301.55; 1.8305 1.46; 1.8238 1.42; 1.8005 0.68; 1.6775 0.67; 1.6666 0.80;1.6450 1.52; 1.6365 1.61; 1.6143 1.47; 1.6060 1.34; 1.5960 0.64; 1.58530.63; 1.5746 0.53; 1.3983 1.42; 1.2358 0.74; 1.1929 3.79; 1.1751 7.42;1.1573 3.71; 0.8902 0.34; −0.0002 2.24 I-38 [DMSO-D₆] 8.1561 7.74;7.8566 0.37; 7.8334 5.18; 7.8152 3.93; 7.7767 5.16; 7.7497 0.35; 7.70805.45; 7.6698 2.67; 7.5071 0.70; 7.5026 0.68; 7.4865 5.18; 7.4671 2.46;7.4480 0.82; 7.3179 1.59; 7.1846 3.56; 7.1638 1.91; 7.0513 1.77; 7.02784.10; 6.9068 3.59; 6.8920 2.12; 5.4675 0.71; 5.4248 2.68; 5.3818 2.65;5.3389 0.85; 4.3976 0.82; 4.3643 0.84; 4.0571 1.06; 4.0393 3.04; 4.02153.33; 4.0038 1.68; 3.9757 0.84; 3.5679 0.65; 3.4497 0.44; 3.4407 0.74;3.4310 0.63; 3.4213 0.94; 3.4119 1.51; 3.4029 1.09; 3.3922 0.91; 3.38271.29; 3.3734 1.16; 3.3106 847.89; 3.2606 1.74; 2.8865 0.63; 2.8590 1.06;2.8271 0.65; 2.6744 0.68; 2.6697 0.90; 2.6652 0.67; 2.6607 0.39; 2.57650.35; 2.5608 1.10; 2.5398 1.95; 2.5228 4.26; 2.5095 50.87; 2.5051 93.57;2.5007 121.23; 2.4963 85.30; 2.4920 42.05; 2.4215 16.00; 2.3809 0.65;2.3656 1.42; 2.3319 0.79; 2.3272 1.23; 2.1795 0.84; 2.1466 1.68; 2.11340.93; 2.0693 0.42; 1.9869 12.96; 1.8882 0.34; 1.8796 0.38; 1.8582 0.69;1.8502 0.73; 1.8273 0.71; 1.8240 0.69; 1.7982 0.33; 1.6711 0.33; 1.66060.39; 1.6385 0.68; 1.6312 0.76; 1.6095 0.70; 1.5999 0.65; 1.3984 0.70;1.2360 0.33; 1.1929 3.60; 1.1751 7.09; 1.1573 3.53; −0.0002 0.86 I-39[DMSO-D₆] 8.0529 2.63; 7.4083 0.69; 7.3873 1.39; 7.3663 0.80; 7.30460.54; 7.1713 1.24; 7.1572 0.83; 7.1539 1.29; 7.1145 1.75; 7.0380 0.63;7.0216 1.35; 6.9734 1.68; 6.9340 1.07; 6.8995 1.24; 6.8857 0.67; 6.76752.92; 6.7464 2.73; 5.7462 2.13; 5.4023 0.98; 5.3669 0.97; 5.2961 0.37;3.7483 0.73; 3.7297 0.96; 3.7183 16.00; 3.6726 0.38; 3.3900 0.39; 3.37100.55; 3.3621 0.81; 3.3520 0.80; 3.3120 148.95; 3.2739 0.52; 3.2692 0.52;3.1774 0.33; 2.8482 0.36; 2.5397 0.32; 2.5093 9.70; 2.5051 17.38; 2.500722.12; 2.4964 15.46; 2.0966 0.55; 2.0691 0.42; 1.9869 0.66; 1.1751 0.38I-40 [DMSO-D₆] 8.1658 16.00; 8.1537 1.38; 8.1463 6.35; 8.1411 3.10;8.1324 7.18; 8.1242 7.06; 8.1155 3.20; 8.1103 6.18; 7.8314 5.38; 7.793410.54; 7.7232 11.07; 7.6852 5.42; 7.4246 6.41; 7.4198 2.50; 7.402512.01; 7.3853 2.51; 7.3804 5.93; 7.3287 0.58; 7.3200 3.34; 7.1867 7.49;7.1659 3.73; 7.0534 3.64; 7.0299 8.05; 6.9096 7.63; 6.8940 4.13; 5.74788.22; 5.4673 1.53; 5.4248 5.92; 5.3843 5.83; 5.3421 1.61; 4.3962 1.81;4.3639 1.89; 4.0579 0.37; 4.0400 1.00; 4.0221 1.56; 4.0047 1.88; 3.97421.86; 3.4467 0.76; 3.4379 1.37; 3.4280 1.08; 3.4184 1.72; 3.4091 2.88;3.3999 1.80; 3.3901 1.27; 3.3804 1.69; 3.3714 1.12; 3.3059 258.95;3.2617 1.92; 2.8898 1.27; 2.8608 2.24; 2.8319 1.28; 2.6751 0.45; 2.67050.58; 2.6661 0.43; 2.5404 1.00; 2.5099 34.49; 2.5058 61.68; 2.501478.48; 2.4972 55.77; 2.3326 0.48; 2.3283 0.60; 2.3235 0.46; 2.1782 1.69;2.1462 3.51; 2.1120 1.96; 2.0707 0.36; 1.9876 3.68; 1.8915 0.62; 1.88090.72; 1.8599 1.47; 1.8518 1.55; 1.8298 1.47; 1.8221 1.38; 1.7999 0.62;1.7897 0.51; 1.6799 0.62; 1.6710 0.77; 1.6497 1.51; 1.6409 1.60; 1.61921.46; 1.6106 1.39; 1.5891 0.59; 1.5794 0.50; 1.1934 1.02; 1.1756 1.98;1.1578 1.00; −0.0002 2.56 I-41 [DMSO-D₆] 8.1966 16.00; 7.9032 4.15;7.8838 4.79; 7.8736 0.65; 7.8076 3.98; 7.7992 2.84; 7.7930 3.32; 7.78932.92; 7.7694 15.05; 7.7407 13.03; 7.7026 3.85; 7.6729 1.85; 7.6584 2.23;7.6527 3.53; 7.6382 3.57; 7.6332 2.61; 7.6186 2.20; 7.5794 0.35; 7.55842.16; 7.5536 1.96; 7.5374 3.17; 7.5320 2.93; 7.5178 1.45; 7.5159 1.46;7.5112 1.36; 7.3183 3.17; 7.2152 0.48; 7.1850 7.11; 7.1646 3.72; 7.05173.54; 7.0286 7.98; 6.9075 7.40; 6.8927 4.12; 5.7472 7.53; 5.4663 1.46;5.4241 5.62; 5.3831 5.56; 5.3407 1.65; 5.3275 0.53; 4.3943 1.71; 4.36161.80; 4.0575 0.36; 4.0398 0.94; 4.0219 1.45; 4.0045 1.76; 3.9740 1.76;3.4478 0.76; 3.4389 1.51; 3.4291 1.10; 3.4199 1.75; 3.4103 2.74; 3.40101.80; 3.3909 1.32; 3.3815 1.84; 3.3721 1.26; 3.3093 504.59; 3.285810.43; 3.2613 2.21; 3.1909 0.40; 3.1817 0.36; 2.8901 1.23; 2.8603 2.16;2.8324 1.25; 2.6750 0.52; 2.6704 0.69; 2.6659 0.54; 2.5403 1.13; 2.509940.78; 2.5057 74.07; 2.5013 95.31; 2.4970 68.09; 2.3327 0.58; 2.32820.75; 2.3233 0.58; 2.1812 1.62; 2.1474 3.34; 2.1138 1.88; 2.0702 0.38;1.9874 3.52; 1.8930 0.64; 1.8834 0.72; 1.8625 1.42; 1.8542 1.49; 1.83151.41; 1.8243 1.34; 1.8023 0.63; 1.7924 0.52; 1.6773 0.63; 1.6680 0.75;1.6468 1.48; 1.6378 1.54; 1.6161 1.44; 1.6072 1.35; 1.5864 0.60; 1.57750.48; 1.2348 0.40; 1.1933 0.98; 1.1755 1.92; 1.1577 0.98; −0.0002 2.25I-42 [DMSO-D₆] 9.6022 0.51; 8.1426 16.00; 8.1000 0.44; 7.6087 1.85;7.6058 2.17; 7.5886 7.11; 7.5868 6.55; 7.5851 6.19; 7.5820 4.73; 7.57724.59; 7.5655 4.35; 7.5606 5.97; 7.5567 3.74; 7.5517 3.37; 7.5462 1.73;7.5411 4.80; 7.5359 7.56; 7.5327 4.36; 7.5119 5.22; 7.5077 5.25; 7.49553.89; 7.4925 4.83; 7.4883 2.58; 7.4762 1.72; 7.4724 1.65; 7.4214 0.33;7.3567 6.58; 7.3442 0.48; 7.3174 11.38; 7.3054 3.64; 7.2919 0.47; 7.212610.79; 7.1726 12.70; 7.1575 4.07; 7.0464 0.85; 7.0388 3.87; 7.0214 8.53;6.9989 0.46; 6.9656 0.43; 6.8997 7.57; 6.8856 4.42; 6.2908 0.40; 6.27540.37; 5.7463 7.66; 5.4482 1.44; 5.4054 5.92; 5.3888 1.38; 5.3685 5.82;5.3261 1.46; 5.2949 0.54; 5.2788 0.55; 4.3552 1.70; 4.3220 1.80; 4.03920.32; 4.0215 0.39; 3.9786 1.58; 3.9462 1.77; 3.6839 0.32; 3.6720 0.36;3.5679 0.70; 3.4728 0.35; 3.4485 0.47; 3.4115 1.95; 3.4019 1.88; 3.39252.79; 3.3835 4.22; 3.3733 3.67; 3.3107 2339.33; 3.2435 3.77; 3.19391.38; 3.1526 0.83; 3.1441 0.81; 3.0746 0.52; 3.0209 0.43; 2.9962 0.35;2.9745 0.36; 2.9605 0.33; 2.9565 0.34; 2.9265 0.35; 2.9100 0.35; 2.87841.39; 2.8524 2.31; 2.8212 1.38; 2.7681 0.33; 2.6955 0.42; 2.6742 1.96;2.6697 2.54; 2.6651 1.88; 2.6192 0.39; 2.5396 4.00; 2.5226 12.06; 2.5093145.42; 2.5050 264.34; 2.5006 339.77; 2.4962 237.87; 2.4920 117.25;2.3747 0.67; 2.3716 0.59; 2.3579 0.58; 2.3497 0.55; 2.3366 1.23; 2.33182.03; 2.3273 2.66; 2.3228 2.02; 2.3019 0.47; 2.2849 0.41; 2.2255 0.33;2.2202 0.34; 2.2162 0.33; 2.1927 0.34; 2.1429 1.76; 2.1103 3.38; 2.06923.06; 1.9869 1.67; 1.9078 0.46; 1.8600 0.75; 1.8515 0.87; 1.8217 1.66;1.7989 1.50; 1.7925 1.40; 1.7706 0.70; 1.7493 0.32; 1.6417 0.36; 1.62690.71; 1.6175 0.84; 1.5959 1.49; 1.5872 1.59; 1.5658 1.48; 1.5573 1.41;1.5359 0.68; 1.3983 0.38; 1.2361 1.25; 1.1928 0.61; 1.1749 1.07; 1.15720.59; 1.0271 0.58; 0.8902 0.42; −0.0002 4.66 I-43 [DMSO-D₆] 8.172014.54; 7.6305 6.14; 7.6255 7.71; 7.6087 16.00; 7.6074 16.00; 7.57458.52; 7.5580 5.31; 7.5511 3.66; 7.5394 0.60; 7.5347 2.63; 7.3074 9.53;7.2679 9.62; 7.1737 6.57; 7.1590 3.22; 7.0746 8.73; 7.0404 3.64; 7.03516.55; 7.0230 7.51; 6.9008 6.24; 6.8871 3.63; 5.7468 9.42; 5.4475 1.13;5.4051 5.10; 5.3719 5.08; 5.3295 1.10; 4.3546 1.43; 4.3212 1.50; 3.98111.35; 3.9467 1.46; 3.4212 0.76; 3.4118 1.24; 3.4020 1.00; 3.3927 1.54;3.3834 2.49; 3.3739 1.67; 3.3640 1.31; 3.3550 1.83; 3.3451 1.62; 3.3057532.18; 3.2430 1.10; 2.8798 0.99; 2.8505 1.73; 2.8229 0.98; 2.6743 0.57;2.6697 0.76; 2.6652 0.57; 2.5397 1.04; 2.5228 3.13; 2.5095 43.31; 2.505180.87; 2.5006 105.64; 2.4962 72.60; 2.4918 34.34; 2.3319 0.51; 2.32740.70; 2.3228 0.49; 2.1460 1.23; 2.1109 2.57; 2.0761 1.48; 2.0697 2.08;1.9871 0.34; 1.8677 0.43; 1.8576 0.52; 1.8371 1.09; 1.8282 1.16; 1.80611.08; 1.7981 1.00; 1.7764 0.44; 1.7668 0.35; 1.6318 0.42; 1.6227 0.53;1.6019 1.10; 1.5928 1.18; 1.5713 1.11; 1.5628 1.06; 1.5420 0.45; 1.53300.36; 0.0080 0.91; −0.0002 21.13; −0.0084 0.80 I-44 [DMSO-D₆] 8.007616.00; 7.5620 7.74; 7.5229 8.94; 7.3109 3.30; 7.1776 7.54; 7.1606 3.72;7.0444 3.71; 7.0246 8.50; 7.0016 8.77; 6.9624 7.56; 6.9033 7.09; 6.88874.24; 5.7458 7.11; 5.4559 1.43; 5.4133 5.52; 5.3717 5.46; 5.3291 1.43;4.3700 1.59; 4.3368 1.68; 4.0395 0.48; 4.0217 0.54; 3.9873 1.51; 3.95261.65; 3.4072 0.82; 3.3978 1.47; 3.3885 1.21; 3.3787 1.90; 3.3692 3.11;3.3597 2.31; 3.3494 2.32; 3.3398 3.75; 3.3125 811.08; 3.2891 6.55;3.2722 3.23; 3.2425 1.55; 2.8735 1.16; 2.8462 2.03; 2.8160 1.18; 2.78900.76; 2.7808 1.11; 2.7718 0.85; 2.7617 1.77; 2.7536 2.28; 2.7453 1.29;2.7344 1.26; 2.7266 1.30; 2.6792 0.32; 2.6744 0.58; 2.6700 0.77; 2.66540.59; 2.5400 1.06; 2.5231 2.82; 2.5098 41.65; 2.5054 78.84; 2.5009103.87; 2.4965 72.41; 2.4921 35.05; 2.3323 0.58; 2.3276 0.74; 2.32300.55; 2.1412 1.46; 2.1087 3.04; 2.0691 2.21; 1.9869 2.02; 1.8576 0.66;1.8486 0.85; 1.8145 4.71; 1.7863 4.49; 1.7557 2.72; 1.7487 3.00; 1.74102.68; 1.7240 3.48; 1.7174 4.43; 1.6634 1.69; 1.6318 2.31; 1.6232 1.88;1.6021 1.41; 1.5927 1.46; 1.5714 1.36; 1.5628 1.29; 1.5420 0.57; 1.53160.47; 1.3981 0.51; 1.3911 0.60; 1.3835 0.81; 1.3603 1.87; 1.3529 2.68;1.3209 4.92; 1.3078 3.17; 1.2903 6.56; 1.2644 2.70; 1.2579 2.99; 1.23461.37; 1.2280 1.35; 1.2204 1.12; 1.2119 0.95; 1.1929 1.76; 1.1898 1.76;1.1817 1.38; 1.1753 1.84; 1.1682 0.93; 1.1576 1.58; 1.1517 0.93; 1.13840.38; 1.1303 0.44; −0.0002 1.84 I-45 [DMSO-D₆] 8.1080 7.57; 7.8502 0.34;7.5392 1.54; 7.5353 1.71; 7.5296 0.62; 7.5187 2.18; 7.5165 2.17; 7.46700.76; 7.4637 0.76; 7.4483 1.94; 7.4450 1.65; 7.4296 1.63; 7.4262 1.46;7.3967 2.30; 7.3577 7.53; 7.3514 2.76; 7.3416 2.36; 7.3319 1.81; 7.32321.13; 7.3115 6.23; 7.2725 2.19; 7.1752 3.35; 7.1676 0.47; 7.1588 1.71;7.0420 1.66; 7.0304 0.42; 7.0227 3.82; 6.9019 3.16; 6.8868 1.93; 5.74582.90; 5.4523 0.59; 5.4097 2.46; 5.3896 0.33; 5.3711 2.44; 5.3292 0.70;4.3626 0.70; 4.3298 0.73; 3.9844 0.65; 3.9506 0.72; 3.4132 0.57; 3.40420.46; 3.3943 0.75; 3.3848 1.24; 3.3755 0.91; 3.3651 0.81; 3.3563 1.21;3.3172 394.60; 3.2752 1.65; 3.2468 0.83; 2.8817 0.52; 2.8509 0.96;2.8238 0.52; 2.6703 0.35; 2.5759 0.78; 2.5429 0.67; 2.5404 0.53; 2.52361.24; 2.5102 19.67; 2.5058 37.43; 2.5013 49.46; 2.4968 34.40; 2.492416.69; 2.4237 0.37; 2.3502 16.00; 2.3327 0.50; 2.3280 0.51; 2.3236 0.39;2.1503 0.67; 2.1166 1.34; 2.0824 0.76; 2.0693 0.65; 1.9871 0.62; 1.83450.60; 1.8276 0.64; 1.8041 0.60; 1.7975 0.55; 1.6048 0.57; 1.5958 0.61;1.5740 0.57; 1.5651 0.55; 1.1753 0.35; −0.0002 5.31 I-46 [DMSO-D₆]8.2538 0.55; 8.2464 2.60; 8.2378 2.12; 8.2347 2.34; 8.2281 1.60; 8.22202.83; 8.1638 3.93; 8.1432 4.27; 8.1115 16.00; 8.0617 2.86; 8.0565 2.00;8.0492 2.57; 8.0456 2.60; 8.0379 3.08; 8.0297 0.58; 7.8844 3.94; 7.88174.05; 7.8667 4.91; 7.8639 4.50; 7.7642 0.76; 7.6727 4.14; 7.6642 0.56;7.6547 4.45; 7.6523 4.57; 7.6423 0.70; 7.6345 4.12; 7.6246 6.02; 7.61904.20; 7.6137 4.57; 7.6106 4.56; 7.6058 4.05; 7.6002 6.58; 7.5888 1.05;7.5827 0.40; 7.5410 1.71; 7.5020 14.99; 7.4927 14.47; 7.4782 0.38;7.4538 1.63; 7.3082 2.72; 7.1749 6.26; 7.1590 3.10; 7.1437 0.43; 7.04173.11; 7.0325 0.86; 7.0230 7.09; 6.9977 0.40; 6.9665 0.52; 6.9025 6.29;6.8871 3.50; 6.7280 0.46; 6.6967 0.38; 5.7462 12.28; 5.4531 1.14; 5.41044.61; 5.3909 0.50; 5.3709 4.52; 5.3284 1.15; 5.2700 0.36; 5.2559 0.36;4.3684 1.31; 4.3351 1.40; 4.0578 0.48; 4.0400 1.47; 4.0222 1.52; 4.00430.79; 3.9874 1.31; 3.9536 1.42; 3.4289 0.57; 3.4196 1.07; 3.4100 0.87;3.4001 1.34; 3.3910 2.26; 3.3817 1.55; 3.3715 1.30; 3.3622 1.96; 3.3196789.08; 3.2752 2.90; 3.2467 1.47; 3.0381 0.49; 2.8795 1.00; 2.8512 2.01;2.8221 0.98; 2.6753 0.48; 2.6709 0.62; 2.6664 0.48; 2.5409 0.77; 2.52412.11; 2.5107 33.80; 2.5063 64.26; 2.5019 84.75; 2.4974 59.16; 2.493028.67; 2.3332 0.51; 2.3285 0.65; 2.3239 0.49; 2.1541 1.23; 2.1216 2.54;2.0873 1.44; 2.0699 0.84; 1.9875 6.45; 1.8702 0.47; 1.8618 0.54; 1.83931.10; 1.8316 1.17; 1.8097 1.10; 1.8017 1.02; 1.7795 0.47; 1.7697 0.41;1.6407 0.45; 1.6312 0.58; 1.6099 1.07; 1.6009 1.16; 1.5794 1.10; 1.57061.03; 1.5491 0.48; 1.5397 0.39; 1.2345 0.60; 1.1933 1.90; 1.1755 3.61;1.1577 1.79; 0.0081 0.37; −0.0002 9.08; −0.0083 0.39 I-47 [DMSO-D₆]8.0468 1.47; 7.5409 0.62; 7.5028 1.01; 7.3802 0.96; 7.3422 0.60; 7.17860.70; 7.1604 0.36; 7.0454 0.35; 7.0244 0.79; 6.9036 0.67; 6.8885 0.41;5.4185 0.50; 5.3705 0.50; 3.3180 74.17; 2.5103 3.27; 2.5059 6.15; 2.50148.08; 2.4970 5.64; 2.4927 2.73; 1.1568 16.00; 1.0780 0.44 I-48 [DMSO-D₆]8.1047 5.08; 7.8248 1.17; 7.8028 2.14; 7.7814 0.98; 7.6546 0.54; 7.65000.56; 7.6164 2.14; 7.6120 2.06; 7.5928 1.97; 7.5860 1.94; 7.5547 0.48;7.5478 0.50; 7.3152 0.97; 7.1819 2.21; 7.1620 1.12; 7.0487 1.09; 7.02592.52; 6.9976 1.12; 6.9916 1.33; 6.9637 0.87; 6.9571 2.99; 6.9508 0.98;6.9354 1.52; 6.9293 1.17; 6.9059 2.12; 6.8901 1.28; 5.7462 1.77; 5.46510.46; 5.4226 1.58; 5.3754 1.60; 5.3330 0.45; 4.3811 0.48; 4.3467 0.50;4.0039 0.41; 3.9974 0.47; 3.9625 0.51; 3.8751 16.00; 3.8388 1.04; 3.56880.58; 3.4328 0.49; 3.4228 0.42; 3.4136 0.63; 3.4043 0.94; 3.3950 0.66;3.3853 0.56; 3.3754 0.74; 3.3659 0.69; 3.3209 214.30; 3.2901 0.87;3.2858 0.87; 3.2541 0.41; 2.8861 0.33; 2.8554 0.58; 2.8286 0.34; 2.54130.33; 2.5245 0.85; 2.5112 10.46; 2.5069 19.22; 2.5024 24.80; 2.498016.91; 2.4936 7.87; 2.1657 0.42; 2.1299 0.85; 2.0948 0.47; 1.9877 0.79;1.8415 0.38; 1.8332 0.39; 1.8105 0.37; 1.8037 0.34; 1.6143 0.38; 1.60610.40; 1.5846 0.38; 1.5756 0.35; 1.1758 0.42; −0.0002 0.46 I-49 [DMSO-D₆]9.6003 0.61; 8.0177 16.00; 7.5816 8.06; 7.5556 8.77; 7.3632 0.40; 7.36050.34; 7.2989 0.38; 7.2743 2.73; 7.2673 0.33; 7.2175 0.34; 7.1857 6.39;7.1784 0.61; 7.1287 3.26; 7.0972 3.11; 7.0605 0.61; 7.0383 7.66; 6.97620.37; 6.9703 0.58; 6.9520 8.89; 6.9480 3.85; 6.9259 7.98; 6.9154 7.06;6.3327 0.60; 6.3226 0.62; 5.4579 2.40; 5.4294 5.41; 5.4039 0.99; 5.37925.39; 5.3644 0.41; 5.3509 2.44; 5.3087 0.77; 5.2972 0.39; 5.2893 0.33;4.3668 1.60; 4.3487 1.64; 4.3448 1.67; 4.1728 0.35; 4.1637 0.34; 3.98011.48; 3.9568 1.62; 3.6698 0.48; 3.6598 0.47; 3.4003 0.60; 3.3941 1.23;3.3879 0.77; 3.3811 1.49; 3.3749 2.61; 3.3685 1.68; 3.3618 1.37; 3.3438592.30; 3.3202 11.51; 3.3150 1.54; 3.3028 2.20; 3.3004 2.26; 3.28844.89; 3.2764 2.49; 3.2740 2.60; 3.2656 2.49; 3.2624 2.60; 3.2465 1.40;3.2426 1.12; 2.8581 1.03; 2.8539 1.46; 2.8363 1.99; 2.8332 2.06; 2.81591.22; 2.8119 1.02; 2.6205 0.45; 2.6176 0.98; 2.6146 1.40; 2.6116 1.01;2.5423 0.52; 2.5239 2.52; 2.5208 3.20; 2.5177 3.15; 2.5088 75.70; 2.5058163.26; 2.5028 224.58; 2.4998 163.62; 2.4968 76.90; 2.3929 0.53; 2.39001.06; 2.3870 1.47; 2.3840 1.07; 2.3811 0.53; 2.1352 1.38; 2.1152 1.65;2.0948 1.52; 2.0768 2.25; 1.9558 2.53; 1.8583 0.73; 1.8509 1.97; 1.84172.34; 1.8364 3.21; 1.8317 2.66; 1.8276 2.78; 1.8206 3.17; 1.8150 3.13;1.8054 1.50; 1.7998 1.58; 1.7937 1.41; 1.7799 0.71; 1.7732 0.63; 1.72190.79; 1.7097 2.70; 1.6972 3.10; 1.6888 2.85; 1.6846 2.05; 1.6766 2.32;1.6662 0.84; 1.6638 0.94; 1.6199 0.33; 1.6008 2.09; 1.5913 6.28; 1.58458.13; 1.5782 10.69; 1.5734 5.83; 1.5679 4.51; 1.5590 2.66; 1.5460 0.99;1.5386 0.78; 1.4972 0.40; 1.4097 1.92; 1.3893 0.44; 1.2336 0.96; 1.17080.45; 1.0236 0.38; 0.0052 0.81; −0.0002 27.57; −0.0057 0.89 I-50[DMSO-D₆] 8.0244 14.36; 7.9983 1.29; 7.6093 6.63; 7.5701 7.63; 7.53100.62; 7.4919 0.67; 7.3112 3.18; 7.1779 7.28; 7.1611 3.67; 7.0446 3.64;7.0354 0.96; 7.0251 8.22; 6.9964 0.61; 6.9733 7.58; 6.9341 6.68; 6.90397.11; 6.8892 4.39; 5.7457 4.24; 5.4559 1.35; 5.4133 5.41; 5.3722 5.38;5.3298 1.43; 5.2957 0.59; 4.3705 1.56; 4.3368 1.70; 4.0396 0.55; 4.02180.62; 3.9878 1.49; 3.9532 1.65; 3.6730 0.43; 3.4016 1.37; 3.3915 1.09;3.3821 1.76; 3.3728 2.86; 3.3631 2.32; 3.3168 815.40; 3.2783 3.69;3.2444 1.84; 2.9482 0.33; 2.9225 0.37; 2.8758 1.20; 2.8455 2.05; 2.81761.15; 2.6750 0.59; 2.6704 0.77; 2.6661 0.56; 2.5493 1.43; 2.5405 1.78;2.5102 39.56; 2.5058 72.67; 2.5013 94.78; 2.4969 66.70; 2.4926 32.43;2.3324 0.52; 2.3280 0.73; 2.3235 0.53; 2.1415 1.50; 2.1088 3.06; 2.06932.13; 1.9871 2.49; 1.8476 0.74; 1.8264 1.44; 1.8184 1.52; 1.7952 1.51;1.7875 1.53; 1.7662 2.67; 1.7362 3.74; 1.7218 4.03; 1.6837 4.30; 1.66772.83; 1.6409 1.91; 1.6328 1.82; 1.6242 1.83; 1.6056 1.81; 1.5722 1.42;1.5641 1.28; 1.5417 0.57; 1.4071 0.41; 1.2632 3.22; 1.2549 3.25; 1.23141.99; 1.2254 1.94; 1.1932 1.69; 1.1753 1.64; 1.1576 0.83; 1.0719 0.61;1.0447 1.44; 1.0189 1.19; 0.9883 0.45; 0.7780 15.77; 0.7621 16.00;0.7414 1.58; −0.0002 1.35 I-51 [DMSO-D₆] 7.6117 0.46; 7.5934 1.32;7.5740 1.93; 7.5557 1.42; 7.5381 0.48; 7.3069 2.68; 7.2107 1.34; 7.20405.75; 7.1829 11.79; 7.1792 12.89; 7.1776 12.89; 7.1738 8.13; 7.16175.80; 7.0403 2.98; 7.0230 6.62; 6.9007 5.78; 6.8871 3.34; 5.4383 1.13;5.3952 4.33; 5.3542 4.38; 5.3115 1.20; 5.2976 0.36; 4.3064 1.34; 4.27441.38; 3.9328 1.27; 3.8993 1.37; 3.4838 1.18; 3.4666 2.41; 3.4496 2.62;3.4325 1.53; 3.4159 0.53; 3.3792 2.18; 3.3621 1.74; 3.3374 3.86; 3.3116292.13; 3.2880 5.08; 3.2679 1.61; 3.2598 1.71; 3.2488 1.23; 3.2391 2.49;3.2309 3.43; 3.2215 1.64; 3.2024 1.86; 3.1296 1.93; 3.1120 1.79; 3.08831.45; 3.0706 1.29; 2.8495 0.87; 2.8420 0.93; 2.8150 1.62; 2.7851 0.91;2.5102 13.21; 2.5059 24.79; 2.5014 32.48; 2.4970 22.75; 2.4927 11.05;2.0699 0.41; 2.0440 1.16; 2.0066 1.78; 1.9635 1.32; 1.7392 0.47; 1.70971.07; 1.6864 1.00; 1.6802 0.96; 1.6566 0.40; 1.6493 0.34; 1.5146 0.48;1.5036 0.45; 1.4845 1.10; 1.4540 1.05; 1.4237 0.42; 1.2883 16.00; 1.271215.74; −0.0002 3.98 I-52 [DMSO-D₆] 8.1450 16.00; 7.9241 0.88; 7.83420.33; 7.8301 0.34; 7.7728 2.13; 7.7685 2.39; 7.7542 4.11; 7.7497 4.60;7.7345 2.55; 7.7303 2.48; 7.7035 1.30; 7.6987 1.27; 7.6901 1.60; 7.68532.71; 7.6823 2.22; 7.6714 2.25; 7.6674 2.23; 7.6644 2.75; 7.6595 1.60;7.6510 1.63; 7.6463 1.35; 7.6221 3.53; 7.6190 3.50; 7.5836 6.54; 7.58066.29; 7.4983 5.45; 7.4922 5.33; 7.4598 2.94; 7.4539 2.87; 7.4088 3.30;7.3968 3.95; 7.3944 4.12; 7.3875 3.63; 7.3830 3.87; 7.3780 6.81; 7.35935.87; 7.3104 3.30; 7.2799 0.41; 7.1772 7.65; 7.1594 3.67; 7.0440 3.77;7.0234 8.21; 6.9281 0.61; 6.9027 7.22; 6.8875 4.01; 5.7458 4.96; 5.45821.60; 5.4166 5.55; 5.3715 5.47; 5.3481 0.78; 5.3291 1.57; 4.3715 1.80;4.3388 1.84; 4.1303 0.35; 4.0392 0.39; 4.0202 0.43; 3.9930 1.81; 3.95981.88; 3.8840 0.33; 3.8496 0.33; 3.8245 0.39; 3.7895 0.39; 3.7752 0.35;3.7579 0.37; 3.7289 0.37; 3.7233 0.37; 3.6965 0.42; 3.6610 0.45; 3.62170.54; 3.5969 0.60; 3.5520 0.72; 3.4287 3.21; 3.4096 4.17; 3.3998 5.68;3.3903 5.36; 3.3708 7.58; 3.3190 2661.98; 3.2498 2.21; 3.2196 0.57;3.2014 0.46; 3.1642 0.33; 2.8811 1.22; 2.8518 2.09; 2.8243 1.26; 2.67501.07; 2.6704 1.30; 2.6657 1.03; 2.5943 0.50; 2.5402 2.29; 2.5101 76.99;2.5057 139.24; 2.5013 178.61; 2.4969 123.40; 2.4926 59.64; 2.4440 0.40;2.3322 0.85; 2.3282 1.16; 2.3235 0.84; 2.1585 1.58; 2.1250 3.07; 2.08522.03; 2.0692 1.31; 1.9868 0.46; 1.8602 0.71; 1.8300 1.49; 1.8091 1.34;1.8014 1.27; 1.7781 0.60; 1.7688 0.55; 1.6302 0.69; 1.6093 1.37; 1.60011.42; 1.5787 1.36; 1.5704 1.30; 1.5477 0.56; 1.5370 0.50; 1.2365 0.54;−0.0002 12.15 I-55 [DMSO-D₆] 8.2161 0.55; 8.0448 12.22; 8.0245 0.94;8.0222 1.08; 7.5743 1.29; 7.5700 1.58; 7.5519 2.58; 7.5491 2.43; 7.53511.79; 7.5306 2.10; 7.4889 2.95; 7.4846 3.06; 7.4699 3.52; 7.4657 3.40;7.4413 0.38; 7.4237 15.38; 7.4226 16.00; 7.4168 2.28; 7.4129 1.63;7.4071 1.54; 7.3832 0.47; 7.3043 2.07; 7.2886 0.59; 7.2762 3.88; 7.25563.38; 7.2039 0.40; 7.1915 0.41; 7.1822 0.70; 7.1709 4.73; 7.1574 2.58;7.1299 2.24; 7.1113 3.88; 7.0945 2.00; 7.0927 2.00; 7.0766 0.42; 7.05500.57; 7.0464 0.76; 7.0377 2.42; 7.0213 5.38; 6.9783 0.33; 6.9548 0.49;6.9007 4.86; 6.8854 3.08; 6.8539 0.53; 6.7244 0.41; 5.7466 1.57; 5.44400.74; 5.4010 3.72; 5.3720 3.77; 5.3580 0.73; 5.3465 0.34; 5.3300 0.85;5.3056 0.36; 5.2957 0.98; 4.9216 9.22; 4.9158 10.09; 4.8789 0.73; 4.87320.75; 4.8116 0.32; 4.8058 0.34; 4.3462 1.07; 4.3106 1.10; 4.2628 0.35;4.2512 0.38; 4.2396 0.39; 4.0218 0.33; 3.9780 1.07; 3.9416 1.11; 3.69730.44; 3.6931 0.44; 3.6841 0.58; 3.6723 0.76; 3.6630 0.54; 3.6508 0.35;3.5793 0.49; 3.5560 2.51; 3.5501 5.43; 3.5442 2.70; 3.5373 0.69; 3.40730.79; 3.3931 1.05; 3.3883 1.12; 3.3794 1.79; 3.3697 1.27; 3.3585 1.26;3.3498 1.63; 3.3074 734.77; 3.2863 8.37; 3.2551 2.26; 3.1387 0.42;3.0369 0.63; 2.9014 0.88; 2.8763 1.52; 2.8492 0.96; 2.8150 0.33; 2.67400.51; 2.6692 0.61; 2.6649 0.47; 2.5744 0.55; 2.5394 0.75; 2.5090 34.19;2.5047 64.65; 2.5002 85.50; 2.4958 60.67; 2.4915 30.30; 2.3315 0.56;2.3269 0.72; 2.3224 0.56; 2.2033 0.50; 2.1583 1.06; 2.1246 1.99; 2.08941.22; 2.0693 0.92; 2.0330 0.41; 1.9867 0.54; 1.8534 0.51; 1.8246 0.97;1.8018 0.91; 1.7728 0.47; 1.6391 0.61; 1.6185 1.06; 1.6096 1.07; 1.58791.10; 1.5802 0.95; 1.5579 0.63; 1.4151 1.04; 1.4082 6.37; 1.3933 0.47;1.3889 0.41; 1.3846 0.34; 1.2654 0.63; 1.2499 0.74; 1.2358 1.21; 1.18220.32; 1.1747 0.38; 1.1085 0.55; 1.0909 1.03; 1.0735 0.51; 0.0079 0.32;−0.0002 5.93 I-57 [DMSO-D₆] 8.1634 13.11; 8.1472 0.76; 7.5710 4.48;7.5319 5.69; 7.5073 0.36; 7.4373 0.57; 7.4241 3.82; 7.4040 5.44; 7.40095.75; 7.3808 3.84; 7.3282 0.89; 7.3111 3.27; 7.3060 1.88; 7.2835 0.77;7.1776 11.64; 7.1653 3.74; 7.1379 3.93; 7.0447 3.27; 7.0293 7.89; 7.01520.64; 6.9934 0.35; 6.9096 7.23; 6.8935 4.18; 5.4580 1.46; 5.4154 5.09;5.3913 0.87; 5.3745 5.11; 5.3554 0.72; 5.3319 1.52; 4.3627 1.46; 4.32991.58; 4.0564 1.19; 4.0386 3.60; 4.0208 3.65; 4.0030 1.43; 3.9843 1.37;3.9494 1.66; 3.9175 0.40; 3.8629 2.49; 3.8203 0.37; 3.8073 0.48; 3.54910.33; 3.3691 454.41; 3.3559 688.63; 3.2715 3.26; 3.2420 1.92; 3.19430.69; 3.1851 0.69; 3.1660 1.21; 3.1448 0.46; 2.8753 1.09; 2.8446 1.91;2.8179 1.18; 2.6822 0.40; 2.6779 0.81; 2.6733 1.07; 2.6688 0.80; 2.66430.39; 2.5434 1.87; 2.5264 3.05; 2.5133 58.45; 2.5088 117.23; 2.5042155.51; 2.4996 111.90; 2.4951 53.73; 2.3401 0.37; 2.3356 0.77; 2.33091.04; 2.3263 0.76; 2.1489 1.33; 2.1120 2.64; 2.0867 1.53; 2.0729 3.43;1.9891 16.00; 1.8606 0.49; 1.8514 0.59; 1.8303 1.16; 1.8217 1.27; 1.79981.17; 1.7909 1.10; 1.7697 0.49; 1.7602 0.45; 1.6289 0.55; 1.6179 0.63;1.5974 1.18; 1.5885 1.27; 1.5667 1.18; 1.5584 1.13; 1.5367 0.51; 1.52660.44; 1.3105 0.53; 1.2439 1.83; 1.2350 1.03; 1.2166 2.36; 1.1930 4.45;1.1752 8.86; 1.1574 4.35; −0.0002 1.64 I-59 [DMSO-D₆] 8.4936 9.05;7.3144 1.47; 7.1811 3.27; 7.1608 1.62; 7.0612 1.55; 7.0551 1.88; 7.04762.64; 7.0404 6.28; 7.0247 4.40; 7.0209 3.64; 7.0058 1.19; 6.9989 0.84;6.9846 0.66; 6.9041 3.26; 6.8889 1.86; 5.7472 1.75; 5.4671 0.69; 5.42392.46; 5.3787 2.48; 5.3356 0.70; 4.5903 0.34; 4.4152 10.64; 4.3748 0.80;4.3413 0.86; 4.0390 0.34; 4.0212 0.44; 4.0039 0.78; 3.9676 0.78; 3.70960.47; 3.7057 0.36; 3.6980 0.55; 3.6960 0.58; 3.6810 0.60; 3.6715 0.37;3.6677 0.41; 3.4979 0.45; 3.4861 0.42; 3.4746 0.85; 3.4639 1.03; 3.45610.61; 3.4462 0.82; 3.4364 1.23; 3.4268 0.75; 3.4179 0.57; 3.4087 0.72;3.3982 0.47; 3.3009 297.63; 3.2772 7.56; 2.9051 0.55; 2.8768 0.95;2.8471 0.57; 2.6732 0.49; 2.6686 0.69; 2.6639 0.51; 2.5386 1.04; 2.508439.69; 2.5041 72.43; 2.4997 93.44; 2.4953 65.59; 2.4910 32.05; 2.34520.39; 2.3310 0.53; 2.3263 0.69; 2.3219 0.51; 2.2393 15.38; 2.2068 0.36;2.1885 0.79; 2.1850 0.78; 2.1726 0.67; 2.1483 1.40; 2.1128 1.01; 2.076816.00; 1.9866 1.34; 1.8627 0.63; 1.8541 0.66; 1.8330 0.61; 1.8258 0.57;1.6385 0.63; 1.6303 0.65; 1.6093 0.60; 1.5996 0.58; 1.2368 0.78; 1.19250.38; 1.1747 0.68; 1.1570 0.36; 0.0079 0.62; −0.0002 11.73; −0.0085 0.51I-60 [DMSO-D₆] 8.3299 0.40; 7.7755 6.73; 7.6623 0.33; 7.3056 1.04;7.2679 0.47; 7.1722 2.36; 7.1569 1.27; 7.0388 1.16; 7.0317 0.56; 7.02112.58; 6.8993 2.66; 6.8854 1.32; 5.7474 1.35; 5.4566 0.56; 5.4132 1.63;5.3601 1.71; 5.3176 0.60; 5.2956 0.47; 5.2746 0.36; 4.3544 0.44; 4.34320.59; 4.3127 0.63; 3.9748 0.57; 3.9354 0.78; 3.9197 0.40; 3.8887 1.04;3.8676 16.00; 3.6860 0.35; 3.6721 0.45; 3.6627 0.36; 3.4247 0.45; 3.37921.14; 3.3008 1113.92; 3.2777 19.21; 3.2076 0.63; 3.1878 0.59; 3.17440.49; 3.1672 0.43; 3.1486 0.39; 2.8868 0.54; 2.8592 0.74; 2.8383 0.35;2.8211 0.50; 2.6925 2.76; 2.6736 4.08; 2.6688 3.15; 2.6642 2.17; 2.65981.18; 2.6255 0.37; 2.6134 0.41; 2.6090 0.44; 2.5388 4.71; 2.5085 159.43;2.5042 286.60; 2.4997 366.70; 2.4953 252.97; 2.4909 121.25; 2.4240 0.76;2.3732 0.38; 2.3676 0.37; 2.3563 0.40; 2.3312 2.00; 2.3265 2.52; 2.32181.83; 2.1289 0.65; 2.1226 0.64; 2.0845 4.97; 2.0694 4.57; 1.9864 0.54;1.7881 0.59; 1.7521 0.51; 1.5951 2.86; 1.5634 2.25; 1.3991 0.42; 1.23680.73; 1.1747 0.51; 1.1577 0.50; 1.1150 2.15; 1.0951 1.38; 1.0060 0.57;0.9835 0.98; 0.9616 0.73; 0.9555 0.77; 0.8901 0.49; 0.0080 2.80; −0.000251.71; −0.0084 2.10; −0.1497 0.32 I-61 [DMSO-D₆] 7.7676 6.50; 7.30030.96; 7.1671 2.26; 7.1545 1.10; 7.0337 1.12; 7.0185 2.56; 6.9655 0.92;6.9483 1.70; 6.9263 1.19; 6.9067 2.05; 6.8964 2.35; 6.8827 1.36; 6.82461.41; 6.8057 0.97; 5.4374 0.51; 5.3940 1.76; 5.3536 1.74; 5.3104 0.49;4.3147 0.63; 4.2815 0.61; 4.0985 4.92; 4.0568 0.38; 4.0389 0.97; 4.02111.02; 4.0034 0.36; 3.9443 0.64; 3.9025 16.00; 3.7095 0.35; 3.6962 0.36;3.6808 0.38; 3.4982 0.39; 3.4752 0.58; 3.4640 0.53; 3.4527 0.53; 3.44430.52; 3.4166 0.67; 3.4003 0.89; 3.3047 1218.33; 3.2814 18.99; 3.21310.65; 3.0832 0.49; 2.8555 0.43; 2.8231 0.72; 2.7949 0.49; 2.6736 1.46;2.6690 1.91; 2.6643 1.44; 2.6602 0.80; 2.6131 0.39; 2.5390 3.14; 2.5087109.72; 2.5044 200.01; 2.4999 258.25; 2.4955 180.12; 2.4912 86.91;2.3311 1.32; 2.3265 1.73; 2.3220 1.17; 2.3174 0.62; 2.2191 10.31; 2.199710.49; 2.0828 0.52; 2.0691 1.44; 2.0478 0.92; 2.0120 0.61; 1.9867 4.02;1.7607 0.47; 1.7301 0.42; 1.5373 0.48; 1.5301 0.45; 1.5074 0.45; 1.39851.31; 1.2364 0.52; 1.1926 1.17; 1.1748 2.17; 1.1570 1.12; 0.8903 0.37;0.0079 1.13; −0.0002 20.73; −0.0084 0.91 I-62 [DMSO-D₆] 8.6244 16.00;8.4920 0.52; 8.0955 4.59; 8.0545 6.27; 7.8260 6.63; 7.7849 4.95; 7.62050.66; 7.6038 1.48; 7.5993 1.46; 7.5828 2.83; 7.5663 1.51; 7.5618 1.74;7.5454 0.79; 7.3139 2.67; 7.2904 4.80; 7.2679 7.01; 7.2461 3.91; 7.18065.94; 7.1610 2.97; 7.0782 0.35; 7.0473 3.04; 7.0250 6.55; 6.9047 5.84;6.8891 3.33; 5.4687 1.21; 5.4263 4.20; 5.3779 4.28; 5.3351 1.26; 5.29590.43; 4.3852 1.32; 4.3523 1.40; 4.0572 1.04; 4.0394 3.11; 4.0216 3.52;4.0039 2.14; 3.9745 1.38; 3.5682 0.36; 3.4991 0.69; 3.4899 1.12; 3.47990.94; 3.4707 1.40; 3.4614 2.23; 3.4520 1.49; 3.4426 1.16; 3.4330 1.50;3.4252 1.10; 3.4115 0.90; 3.3151 1941.32; 3.1796 0.72; 3.1408 0.67;2.9072 1.09; 2.8782 1.77; 2.8506 1.14; 2.8302 0.33; 2.6956 0.39; 2.67950.76; 2.6749 1.36; 2.6702 1.76; 2.6658 1.33; 2.6612 0.76; 2.5402 3.49;2.5233 8.22; 2.5099 97.98; 2.5056 183.21; 2.5011 241.25; 2.4967 173.04;2.4923 86.93; 2.3804 0.38; 2.3491 0.35; 2.3323 1.45; 2.3278 1.79; 2.32331.42; 2.1993 1.36; 2.1620 2.48; 2.1238 1.57; 2.0851 0.33; 2.0694 2.27;1.9871 13.50; 1.9085 0.86; 1.8950 0.53; 1.8854 0.62; 1.8636 1.17; 1.85651.25; 1.8330 1.17; 1.8256 1.14; 1.8047 0.55; 1.7953 0.50; 1.6675 0.61;1.6469 1.16; 1.6376 1.25; 1.6157 1.15; 1.6072 1.11; 1.5860 0.52; 1.57640.47; 1.3984 0.42; 1.2355 0.71; 1.1930 3.81; 1.1753 7.51; 1.1575 3.69;0.0079 0.46; −0.0002 9.48; −0.0085 0.45 I-63 [DMSO-D₆] 8.1046 3.68;7.3058 0.73; 7.2811 0.75; 7.2622 1.16; 7.2431 1.07; 7.1725 1.68; 7.15820.89; 7.1374 2.66; 7.1301 1.34; 7.1186 1.96; 7.0904 3.04; 7.0561 2.91;7.0392 0.87; 7.0221 1.91; 7.0166 1.02; 6.9007 1.65; 6.8863 0.91; 5.40291.36; 5.3696 1.32; 4.3529 0.40; 4.3211 0.42; 4.0573 0.42; 4.0395 1.20;4.0217 1.22; 4.0038 0.46; 3.9768 0.38; 3.9445 0.42; 3.3995 0.60; 3.39020.62; 3.3808 0.83; 3.3713 1.19; 3.3608 1.19; 3.3132 179.92; 3.2393 0.40;2.8479 0.49; 2.5398 0.71; 2.5096 16.90; 2.5053 30.21; 2.5009 38.39;2.4966 26.71; 2.4923 12.94; 2.1841 0.47; 2.1360 16.00; 2.1043 0.77;2.0695 0.51; 1.9870 5.09; 1.8196 0.33; 1.5817 0.32; 1.3982 0.54; 1.19291.40; 1.1752 2.76; 1.1573 1.35; −0.0002 0.40 I-64 [DMSO-D₆] 11.44444.39; 11.1901 0.81; 9.8995 0.61; 9.0748 0.34; 8.6602 0.56; 7.9819 0.34;7.8239 1.45; 7.7835 1.56; 7.6641 0.87; 7.6598 0.95; 7.6444 1.02; 7.64040.97; 7.6203 2.89; 7.6118 0.37; 7.6004 2.97; 7.5921 0.47; 7.5795 0.71;7.5283 0.70; 7.4820 0.52; 7.4651 1.27; 7.4613 1.12; 7.4428 1.44; 7.42570.56; 7.4216 0.56; 7.3257 0.38; 7.3187 0.66; 7.3051 0.81; 7.2482 0.43;7.2196 1.03; 7.2109 2.00; 7.1990 1.13; 7.1919 2.15; 7.1884 2.39; 7.17142.69; 7.1462 0.37; 7.0881 0.41; 7.0802 1.14; 7.0690 0.56; 7.0608 2.03;7.0526 1.09; 7.0426 1.41; 7.0388 1.54; 7.0349 2.49; 7.0276 1.94; 6.90912.84; 6.8913 0.96; 6.3120 1.53; 6.2723 1.45; 6.1958 0.37; 6.1870 0.76;6.1688 0.61; 5.7851 0.68; 5.7646 0.79; 5.7573 1.82; 5.7375 0.50; 5.47130.46; 5.4445 0.43; 5.4276 1.10; 5.4027 1.31; 5.3905 0.78; 5.3807 1.73;5.3669 1.21; 5.3376 0.51; 5.3260 0.44; 5.0197 0.55; 5.0141 0.57; 4.90422.67; 4.8986 2.60; 4.8296 0.71; 4.8208 0.86; 4.8045 2.17; 4.7984 2.25;4.7687 0.39; 4.7639 0.42; 4.3678 0.52; 4.3440 0.75; 4.3274 0.56; 4.05530.78; 4.0374 2.23; 4.0197 2.26; 4.0018 0.77; 3.9550 0.68; 3.8317 0.39;3.8045 0.41; 3.7879 0.78; 3.7614 0.68; 3.7015 0.68; 3.6923 0.45; 3.68060.63; 3.6583 0.34; 3.6384 0.38; 3.6124 0.86; 3.6067 2.11; 3.6010 0.87;3.5675 0.69; 3.5118 1.03; 3.5061 2.16; 3.5001 0.92; 3.4144 0.39; 3.40150.59; 3.3913 0.99; 3.3795 1.66; 3.3470 1964.81; 3.3250 5.70; 3.29721.40; 3.2599 1.04; 3.2431 0.82; 3.2282 0.61; 3.2018 0.33; 2.8662 0.42;2.8307 0.70; 2.8039 0.50; 2.6768 1.01; 2.6718 1.53; 2.6673 1.15; 2.54210.78; 2.5251 2.65; 2.5206 3.84; 2.5112 86.20; 2.5071 166.76; 2.5028232.18; 2.4986 160.26; 2.4944 80.12; 2.4562 0.37; 2.3342 1.12; 2.32951.39; 2.3251 1.04; 2.1407 0.58; 2.1029 1.02; 2.0746 16.00; 2.0457 0.53;1.9892 10.59; 1.8258 0.58; 1.7937 0.54; 1.7670 0.43; 1.7581 0.43; 1.59380.34; 1.5805 0.39; 1.5736 0.52; 1.5644 0.52; 1.5448 0.62; 1.2346 0.73;1.1922 2.79; 1.1744 5.96; 1.1567 2.76; 0.0079 0.59; −0.0002 20.96;−0.0087 0.56 I-65 [CD₃CN] 8.0859 4.04; 7.8317 3.92; 7.8312 3.99; 7.69100.33; 7.6866 0.33; 7.6476 1.02; 7.6434 1.12; 7.6283 1.07; 7.6241 1.11;7.5577 0.89; 7.5556 1.56; 7.5534 0.79; 7.5395 0.82; 7.5368 0.92; 7.53500.83; 7.5323 0.74; 7.5185 0.85; 7.5139 0.73; 7.1323 1.29; 7.1122 1.16;7.0765 0.89; 7.0741 0.85; 7.0575 1.35; 7.0557 1.19; 7.0390 0.79; 7.03660.71; 7.0124 0.43; 7.0047 0.33; 6.9912 0.42; 6.9858 0.49; 6.9674 0.35;6.9022 1.35; 6.3609 2.00; 5.4215 10.07; 5.0391 1.26; 5.0021 0.57; 3.94980.56; 3.8868 16.00; 3.8073 4.63; 3.7942 1.21; 3.3556 0.49; 3.3456 0.35;3.3381 0.57; 3.3281 0.99; 3.3181 0.58; 3.3108 0.41; 3.3009 0.58; 3.28990.44; 2.2310 12.74; 2.2294 10.23; 2.1955 0.52; 2.1638 0.59; 2.0857 0.36;1.9912 41.03; 1.9596 1.75; 1.9524 1.81; 1.9428 7.37; 1.9367 4.93; 1.930719.09; 1.9246 33.26; 1.9184 43.17; 1.9123 29.21; 1.9061 14.83; 1.74690.34; 1.2802 0.39; 1.2203 0.34; 1.2026 0.74; 1.1847 0.39; 0.9161 0.44;−0.0001 4.75

The intensity of sharp signals correlates with the height of the signalsin a printed example of an NMR spectrum in cm and shows the true ratiosof the signal intensities. In the case of broad signals, a plurality ofpeaks or the middle of the signal and their relative intensitiescompared to the most intensive signal in the spectrum may be shown.

The lists of the ¹H-NMR peaks are similar to the classic ¹H-NMR printsand thus usually comprise all peaks listed in classic NMRinterpretations.

In addition, like classic ¹H-NMR prints, they may show solvent signals,signals of stereoisomers of the target compounds, which are likewisepart of the subject matter of the invention, and/or peaks of impurities.

In the list of compound signals in the delta range of solvents and/orwater, in our lists of ¹H-NMR peaks the usual solvent peaks, for examplepeaks of DMSO in DMSO-d₆ and the peak of water, which usually on averagehave a high intensity, are shown.

Usually, on average, the peaks of stereoisomers of the target compoundsand/or peaks of impurities have a lower intensity than the peaks of thetarget compounds (for example with a purity of >90%).

Such stereoisomers and/or impurities may be typical for the preparationprocess in question. Thus, their peaks may help to identify anyreproduction of our preparation process using “by-product fingerprints”.

If required, an expert calculating the peaks of the target compoundswith known methods (MestreC, ACD simulation, but also using empiricallyevaluated expected values) can isolate the peaks of the targetcompounds, using, if appropriate, additional intensity filters. Thisisolation would be similar to the corresponding peak picking of theclassic ¹H-NMR interpretation.

Use Examples Example A

Phytophthora Test (Tomato)/Protective

Solvent: 49 parts by weight of N,N-dimethylformamide Emulsifier:  1 partby weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young tomato plants are sprayed withthe preparation of active compound at the stated application rate. 1 dayafter the treatment, the plants are inoculated with a spore suspensionof Phytophthora infestans and then remain at 100% relative humidity and22° C. for 24 h. The plants are then placed in a climatized cabin atabout 96% relative atmospheric humidity and a temperature of about 20°C.

Evaluation is carried out 7 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

In this test, the following compounds according to the invention I-2,I-3, I-4, I-5, I-6, I-7, I-8, I-11, I-13, I-14, I-15, I-17, I-18, I-19,I-20 and I-21 show, at an active compound concentration of 500 ppm, anefficacy of 70% or more.

Furthermore, in this test the following compounds show, at an activecompound concentration of 500 ppm, an efficacy of 70% or more, where theefficacies reported in brackets are observed for specific compounds:I-16 (80%), I-22 (100%), I-23 (70%), I-24 (94%), I-25 (100%), I-29(100%), I-30 (95%), I-33 (95%), I-34 (95%), I-35 (95%), I-36 (100%),I-37 (95%), I-38 (95%), I-39 (90%), I-41 (95%), I-42 (100%), I-43 (90%),I-44 (95%), I-45 (95%), I-46 (95%), I-47 (94%), I-48 (94%), I-49 (90%),I-50 (95%), I-51 (98%), I-52 (98%), I-53 (90%), I-54 (85%), I-55 (98%),I-57 (98%), I-60 (95%), I-61 (95%), I-65 (93%).

Example B

Plasmopara Test (Grapevine)/Protective

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight ofdimethylacetamide Emulsifier:   1 part by weight of alkylaryl polyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of Plasmopara viticola and then remain in an incubationcabin at about 20° C. and 100% relative atmospheric humidity for 1 day.The plants are then placed in a greenhouse at about 21° C. and about 90%atmospheric humidity for 4 days. The plants are then moistened andplaced in an incubation cabin for 1 day.

Evaluation is carried out 6 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

In this test, the following compounds according to the invention I-3,I-11, I-13, I-14, I-16, I-17, I-18, I-19, I-20, I-21 show, at an activecompound concentration of 100 ppm, an efficacy of 70% or more.

Furthermore, in this test the following compounds show, at an activecompound concentration of 500 ppm, an efficacy of 70% or more, where theefficacies reported in brackets are observed for specific compounds:I-22 (100%), I-24 (100%), I-25 (96%), I-29 (95%), I-30 (85%), I-33(89%), I-34 (84%), I-35 (89%), I-36 (96%), I-42 (90%), I-43 (100%), I-44(74%), I-45 (100%), I-46 (100%), I-49 (79%), I-50 (93%), I-51 (100%),I-52 (94%), I-53 (76%), I-55 (100%), I-57 (91%).

The invention claimed is:
 1. A method for controlling phytopathogenicharmful fungi, the method comprises administering an effective amount ofat least one compound of formula (I′),

wherein: A represents phenyl which may contain up to two substituents,wherein the substituents independently of one another are selected fromR², and R² represents: methyl, ethyl, iodine, chlorine, bromine,fluorine, methoxy, ethoxy, difluoromethyl, or trifluoromethyl, or Arepresents pyrazol-1-yl which, may contain up to two substituents atcarbon, wherein the substituents independently of one another areselected from R³, and R³ represents methyl, difluoromethyl, ortrifluoromethyl, T is selected from the group consisting of*—C(═O)CH₂—#, *—C(═O)CH₂C(CH₃)₂—#, *—C(═O)CH₂CH₂—#, *—C(═O)CH═CH—#,*—C≡CC(═O)—#, *—CH═CHC(═O)—#, *CH₂CH₂C(═O)—#, *—C(═NOCH₃)CH₂—#,*—CH═CHC(NOH)—#, *—C(Cl)═CHC(═O)—#, and *—CH(CH₃)CH₂C(═O)—#, where thebond identified by * is attached directly to G and where the bondidentified by # is attached directly to R¹, R¹ is selected from thegroup consisting of R¹ _(a), R¹ _(b), R¹ _(c), R¹ _(d), R¹ _(e), and R¹_(f), wherein R¹ _(a) represents 1,1-dimethylethyl, R¹ _(b) representscyclohexyl, cyclopentyl, 2-methylcyclohexyl, 3-methylcyclohexyl, or4-methylcyclohexyl, R¹ _(c) represents cyclohex-3-en-1-yl orcyclohex-2-en-1-yl, R¹ _(d) represents phenyl that may contain up to twosubstituents, wherein the substituents independently of one another areselected from R¹², and R¹² represents: chlorine, fluorine, bromine,iodine, methyl, methoxy, ethoxy, trifluoromethyl, difluoromethyl,2-propenyloxy, 2-propynyloxy or phenyl, R¹ _(e) representsnaphthalen-1-yl, naphthalen-2-yl, 1,2,3,4-tetrahydronaphthalen-1-yl,1,2,3,4-tetrahydronaphthalen-2-yl, 5,6,7,8-tetrahydronaphthalen-1-yl,5,6,7,8-tetrahydronaphthalen-2-yl, decalin-1-yl, decalin-2-yl,1H-inden-1-yl, 1H-inden-2-yl, 1H-inden-3-yl, 1H-inden-4-yl,1H-inden-5-yl, 1H-inden-6-yl, 1H-inden-7-yl, indan-1-yl, indan-2-yl,indan-3-yl, indan-4-yl, or indan-5-yl, R¹ _(f) represents furan-2-yl,furan-3-yl, thiophen-2-yl, thiophen-3-yl, isoxazol-3-yl, isoxazol-4-yl,isoxazol-5-yl, pyrrol-1-yl, pyrrol-2-yl, pyrrol-3-yl, oxazol-2-yl,oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl,isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, pyrazol-1-yl,pyrazol-3-yl, pyrazol-4-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl,1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl, 1,2,3-triazol-4-yl,1,2,4-triazol-1-yl, 1,2,4-triazol-3-yl, 1,2,4-triazol-4-yl,pyridin-2-yl, pyridin-3-yl, pyridin-4-yl pyridazin-3-yl, pyridazin-4-yl,pyrimidin-2-yl, pyrimidin-4-yl, or pyrimidin-5-yl, or an agrochemicallyactive salt thereof.
 2. The method of claim 1, wherein: A represents5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl, T represents *—C≡CC(═O)—#,where the bond identified by * is attached directly to G and where thebond identified by # is attached directly to R¹, and R¹ representsnaphthalen-1-yl.
 3. A method for treating a seed, a transgenic plant ora part thereof, the method comprises administering an effective butnon-phytotoxic amount of at least one compound of formula (I′),

wherein: A represents phenyl which may contain up to two substituents,wherein the substituents independently of one another are selected fromR², and R² represents: methyl, ethyl, iodine, chlorine, bromine,fluorine, methoxy, ethoxy, difluoromethyl, or trifluoromethyl, or Arepresents pyrazol-1-yl which may contain up to two substituents atcarbon, wherein the substituents independently of one another areselected from R³, and R³ represents methyl, difluoromethyl, ortrifluoromethyl, T is selected from the group consisting of*—C(═O)CH₂—#, *—C(═O)CH₂C(CH₃)₂—#, *—C(═O)CH₂CH₂—#, *—C(═O)CH═CH—#,*—C≡CC(═O)—#, *—CH═CHC(═O)—#, *CH₂CH₂C(═O)—#, *—C(═NOCH₃)CH₂—#,*—CH═CHC(NOH)—#, *—C(Cl)═CHC (═O)—#, and *—CH(CH₃)CH₂C(═O)—#, where thebond identified by * is attached directly to G and where the bondidentified by # is attached directly to R¹, R¹ is selected from thegroup consisting of R¹ _(a), R¹ _(b), R¹ _(c), R¹ _(d), R¹ _(e), and R¹_(f), wherein R¹ _(a) represents 1,1-dimethylethyl, R¹ _(b) representscyclohexyl, cyclopentyl, 2-methylcyclohexyl, 3-methylcyclohexyl, or4-methylcyclohexyl, R¹ _(c) represents cyclohex-3-en-1-yl orcyclohex-2-en-1-yl, R¹ _(d) represents phenyl that may contain up to twosubstituents, wherein the substituents independently of one another areselected from R¹², and R¹² represents: chlorine, fluorine, bromine,iodine, methyl, methoxy, ethoxy, trifluoromethyl, difluoromethyl,2-propenyloxy, 2-propynyloxy, or phenyl, R¹ _(e) representsnaphthalen-1-yl, naphthalen-2-yl, 1,2,3,4-tetrahydronaphthalen-1-yl,1,2,3,4-tetrahydronaphthalen-2-yl, 5,6,7,8-tetrahydronaphthalen-1-yl,5,6,7,8-tetrahydronaphthalen-2-yl, decalin-1-yl, decalin-2-yl,1H-inden-1-yl, 1H-inden-2-yl, 1H-inden-3-yl, 1H-inden-4-yl,1H-inden-5-yl, 1H-inden-6-yl, 1H-inden-7-yl, indan-1-yl, indan-2-yl,indan-3-yl, indan-4-yl, or indan-5-yl, R¹ _(f) represents furan-2-yl,furan-3-yl, thiophen-2-yl, thiophen-3-yl, isoxazol-3-yl, isoxazol-4-yl,isoxazol-5-yl, pyrrol-1-yl, pyrrol-2-yl, pyrrol-3-yl, oxazol-2-yl,oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl,isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, pyrazol-1-yl,pyrazol-3-yl, pyrazol-4-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl,1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl, 1,2,3-triazol-4-yl,1,2,4-triazol-1-yl, 1,2,4-triazol-3-yl, 1,2,4-triazol-4-yl,pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl,pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, or pyrimidin-5-yl, or anagrochemically active salt thereof.
 4. The method of claim 3, wherein: Arepresents 5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl, T represents*—C≡CC(═O)—#, where the bond identified by * is attached directly to Gand where the bond identified by # is attached directly to R¹, and R¹represents naphthalen-1-yl.
 5. The method of claim 3, wherein thetransgenic plant or the part thereof is selected from the groupconsisting of a transgenic plant or a part thereof, and a germinatingtransgenic plant or a part thereof.
 6. The method of claim 5, whereinthe transgenic plant or the part thereof is a germinating transgenicplant or a part thereof.
 7. The method of claim 3, wherein the seedbeing treated is a transgenic seed that comprises at least oneheterologous gene encoding a polypeptide having insecticidal properties.8. The method of claim 7, wherein the effective but non-phytotoxicamount comprises from 2 to 200 g per 100 kg of seed.
 9. The method ofclaim 6, wherein the effective but non-phytotoxic amount comprises from0.1 to 10,000 g/ha.
 10. The method of claim 3, wherein the method is forcontrolling phytopathogenic fungi infection of the seed, the transgenicplant or a part thereof.
 11. A process for preparing a composition, theprocess comprises mixing at least one compound of formula (I′) or anargochemically active salt thereof, with at least one extender, at leastone surfactant, or a combination thereof,

wherein A represents phenyl which may contain up to two substituents,wherein the substituents independently of one another are selected fromR², and R² represents: methyl, ethyl, iodine, chlorine, bromine,fluorine, methoxy, ethoxy, difluoromethyl, or trifluoromethyl, or Arepresents pyrazol-1-yl, which may contain up to two substituents atcarbon, wherein the substituents independently of one another areselected from R³, and R³ represents methyl, difluoromethyl, ortrifluoromethyl, T is selected from the group consisting of*—C(═O)CH₂—#, *—C(═O)CH₂C(CH₃)₂—#, *—C(═O)CH₂CH₂—#, *—C(═O)CH═CH—#,*—C≡CC(═O)—#, *—CH═CHC(═O)—#, *—CH₂CH₂C(═O)—#, *—C(═NOCH₃)CH₂—#,*—CH═CHC(═NOH)—#, *—C(Cl)═CHC (═O)—#, and *—CH(CH₃)CH₂C(═O)—#, where thebond identified by * is attached directly to G and where the bondidentified by # is attached directly to R¹, R¹ is selected from thegroup consisting of R¹ _(a), R¹ _(b), R¹ _(c), R¹ _(d), R¹ _(e), and R¹_(f), wherein R¹ _(a) represents 1,1-dimethylethyl, R¹ _(b) representscyclohexyl, cyclopentyl, 2-methylcyclohexyl, 3-methylcyclohexyl, or4-methylcyclohexyl, R¹ _(c) represents cyclohex-3-en-1-yl orcyclohex-2-en-1-yl, R¹ _(d) represents phenyl that may contain up to twosubstituents, wherein the substituents independently of one another areselected from R¹² and R¹² represents: chlorine, fluorine, bromine,iodine, methyl, methoxy, ethoxy, trifluoromethyl, difluoromethyl,2-propenyloxy, 2-propynyloxy or phenyl, R¹ _(e)representsnaphthalen-1-yl, naphthalen-2-yl, 1,2,3,4-tetrahydronaphthalen-1-yl,1,2,3,4-tetrahydronaphthalen-2-yl, 5,6,7,8-tetrahydronaphthalen-1-yl,5,6,7,8-tetrahydronaphthalen-2-yl, decalin-1-yl, decalin-2-yl,1H-inden-1-yl, 1H-inden-2-yl, 1H-inden-3-yl, 1H-inden-4-yl,1H-inden-5-yl, 1H-inden-6-yl, 1H-inden-7-yl, indan-1-yl, indan-2-yl,indan-3-yl, indan-4-yl, or indan-5-yl, and R¹ _(f) representsfuran-2-yl, furan-3-yl, thiophen-2-yl, thiophen-3-yl, isoxazol-3-yl,isoxazol-4-yl, isoxazol-5-yl, pyrrol-1-yl, pyrrol-2-yl, pyrrol-3-yl,oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol4-yl,thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl,pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, imidazol-1-yl, imidazol-2-yl,imidazol-4-yl, 1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl,1,2,3-triazol-4-yl, 1,2,4-triazol-1-yl, 1,2,4-triazol-3-yl,1,2,4-triazol-4-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl,pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, orpyrimidin-5-yl.
 12. The process of claim 11, wherein A representspyrazol-1-yl, which may contain up to two substituents at carbon,wherein the substituents independently of one another are selected fromR³, and R³ represents methyl, difluoromethyl, or trifluoromethyl. 13.The process of claim 11, wherein A represents phenyl which may containup to two substituents, wherein the substituents independently of oneanother are selected from R², and R² represents: methyl, ethyl, iodine,chlorine, bromine, fluorine, methoxy, ethoxy, difluoromethyl, ortrifluoromethyl.
 14. The process of claim 12, wherein R¹ is selectedfrom the group consisting of cyclohexyl, phenyl, 2-methoxyphenyl,4-methoxyphenyl, 2-ethoxyphenyl, naphthalen-1-yl, tert-butyl,thiophen-2-yl, furan-2-yl, 2-chlorophenyl, 2,4-dichlorophenyl,2-bromophenyl, 2,6-difluorophenyl, 2-iodophenyl, 2-methylphenyl,3-methylphenyl, cyclopentyl, 2-fluoro-4-methoxyphenyl,2-bromo-4-fluorphenyl, 2,6-dimethoxyphenyl, 2-methylcyclohexyl,2-(prop-2-yn-1-yloxy)phenyl, 2,6-dichlorophenyl, 2,6-dimethylphenyl,2,4,6-trifluorophenyl, 2-chloro-5- fluorophenyl,2-chloro-6-fluorophenyl, 4-fluorophenyl, 3-fluorophenyl, and2-fluorophenyl.
 15. The process of claim 13, wherein R¹ is selected fromthe group consisting of cyclohexyl, phenyl, 2-methoxyphenyl,4-methoxyphenyl, 2-ethoxyphenyl, naphthalen-1-yl, tert-butyl,thiophen-2-yl, furan-2-yl, 2-chlorophenyl, 2,4-dichlorophenyl,2-bromophenyl, 2,6-difluorophenyl, 2-iodophenyl, 2-methylphenyl,3-methylphenyl, cyclopentyl, 2-fluoro-4-methoxyphenyl,2-bromo-4-fluorphenyl, 2,6-dimethoxyphenyl, 2-methylcyclohexyl,2-(prop-2-yn-1-yloxy)phenyl, 2,6-dichlorophenyl, 2,6-dimethylphenyl,2,4,6-trifluorophenyl, 2-chloro-5-fluorophenyl, 2-chloro-6-fluorophenyl,4-fluorophenyl, 3-fluorophenyl, and 2-fluorophenyl.
 16. The process ofclaim 11, wherein: A represents5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl, T represents *—C≡CC(═O)—#,where the bond identified by * is attached directly to G and where thebond identified by # is attached directly to R¹, and R¹ representsnaphthalen-1-yl.
 17. The process of claim 11, wherein the compositioncomprising between 0.05% and 99% by weight of the at least one compoundof formula (I).
 18. The process of claim 11, wherein the at least onesurfactant comprises at least one nonionic surfactant, at least oneanionic surfactant, or a combination thereof.
 19. The process of claim18, wherein the at least one nonionic surfactant is selected from thegroup consisting of ethylene oxide and propylene oxide block polymers,alkylphenol polyglycol ethers, tristryryphenol pilyglycol ethers,phosphate derivatives thereof, and sulfated derivatives thereof.